JPS6140316B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to certain novel solutions that are particularly useful for bonding one material to another, particularly one metal to another. U.S. Patent Application No. 319672 and corresponding Japanese Patent Application No. 57-3980 filed at the same time as the present application.
57-174495), a second conductive material is placed in contact with an adjacent surface of the first conductive material,
the second electrically conductive material is in the form of a dissociable solution, and applying an intermittent electrical signal of a predetermined frequency to the first and second materials, thereby causing the second material to A method of fusing a second metal or conductive material into or onto a first metal or other conductive material is described, the method comprising: fusing a second metal or other conductive material into or onto a first metal or other conductive material. According to this method, the solution of the second material is aqueous or organic. Preferably, an aqueous solution is used, it has a PH of 0.4-14, the amount of the second material in it is in the range of 0.10-10% by weight of the solution, and the resistance of this solution is 10-80 ohm cm is within the range of Preferably both the first and second materials are metal. For example, the first material is iron or an iron alloy and the second material is molybdenum, tungsten or indium. A wide variety of ferrous and/or non-ferrous combinations are possible. As indicated, one embodiment of the method shown in U.S. Patent Application No. 319,672 as well as U.S. Patent Application No. 224,762 involves the use of a metal to be fused to another metal (hereinafter "first" metal). (hereinafter "second metal"), the term "metal" should be understood to mean not only a single metal but also an alloy of metals. US Patent Application No. 224,762 and another US Patent Application No. 319,678 also disclose other methods of fusing metals, where both metal components are solids.
Japanese Patent Application No. 57-3981 (see Japanese Patent Application Laid-Open No. 57-174496) This other method can be conveniently referred to as a "solid-to-solid" method. However, the present invention
It concerns only solutions used in other methods in which one of the metals to be fused is initially in the form of a solution. For convenience, this is referred to as a "liquid-to-solid" scheme. As used herein, the term "fusion" refers to a second metal in a matrix of a first metal.
Refers to penetration by metal atoms or molecules (solid-state diffusion). As used herein, "electrical signal" refers to a pulsed current of a predetermined frequency range. Certain of the metal solutions disclosed in US Patent Application No. 319,672 and others described herein are new and form the basis of the present invention. Broadly speaking, these solutions are aqueous and contain approximately 0.4 to 14
PH, has a resistance of 10-80 ohm cm, and contains the following components: (1) a compound of a dissociable polyvalent metal to be fused to another metal, (2) a compound complexed with Possible compounds, compound (1) and
(2) is soluble in water or forms a water-soluble complex. (3) a stabilizer that functions to keep (1) and (2) and their complexes in solution; (4) a stabilizer that accelerates the reaction rate and reduces the valence of the polyvalent metal to a lower valency; A catalyst that has the function of catalyzing the complexing action between (1) and (2). acidic and/or
Alternatively, use an alkaline substance to ensure the appropriate pH for the usage conditions, and use metal compounds (1) and
It can also help keep (2) in solution. Some of these solutions may contain a sufficient amount of organic solvent to ensure dissolution of the metal and/or complex. Some other solutions require conductivity enhancers. And depending on the desired end result, brighteners can also be present. Wetting agents or surfactants can also be added. By using these solutions, U.S. Patent Application No.
It has been discovered that it is possible to efficiently and economically fuse molten metal with a first metal at ambient temperature using the method described in No. 319,672. These and other objects and aspects of the invention will become apparent from the following description and drawings. The drawings illustrate certain specific embodiments of these solutions of the invention. In the drawings, which are graphs in Figures 51-50, the vertical axis is logarithmic and the horizontal axis is straight. In these graphs, the surface layer was taken as the point where the concentration (wt%) of the matrix and the elements fused thereto were both 50%, as shown by projection. Referring to FIGS. 1 and 2, these figures illustrate in a schematic perspective view an apparatus according to the invention used to carry out the method of the invention. In FIG. 1, the solid-to-solid method is illustrated, where numeral 10 is the power supply and numeral 11 is the oscillator. One side of the output of the oscillator is connected to an electrode 13 via a holder 12. The holder 12 has a rotation check and a trigger for controlling the rotation speed of the electrode 13. The rotation speed is
It is variable between 5000 and 10000 rpm. Electrode 13 is composed of the material to be fused with the matrix. The matrix or support on which the method is carried out and to be treated is designated 14. The matrix is also connected by clamp 15 and line 16 to the other side of the oscillator output. When these connections provide a signal,
The electrodes are positively charged and the matrix is negatively charged. In FIG. 2, corresponding components are labeled with corresponding numbers. However, in this embodiment, the method used is characterized as a liquid-to-solid method. In this device, the material to be fused is in the form of a solution and is held in a container 17. The container 17 is connected to the electrode 19 by a tube 18. The electrode 19 is a plate with an insulating handle 20 through which one side of the output of the oscillator 11 is connected. This output is electrode 1
9 into the main channel 21. Channel 21 has a series of side channels 22 that open to the underside of electrode 20 . Flow from container 17 is by gravity or pump and by handle 20
It can be controlled by a valve such as No. 23. For further control, to ensure uniform distribution of the solution, and to prevent the inclusion of foreign substances, the surface of the electrode 19 is preferably covered with a permeable membrane, such as cotton or nylon. It has been found that it is necessary to apply 50,000 watts/cm ² or a current of the order of 10,000 amperes/cm ² to effect fusion. From a practical point of view, 10,000 amperes/cm ² cannot be constantly applied to the matrix to be treated without damage. However, having a magnitude of 3 amps
It has been found practical to apply a pulsed signal of 2.5 microseconds to 28.6 nanoseconds to the electrodes, and this fuses an area of approximately 0.3 ^mm2 . To fuse the sections of the apparatus shown in FIG. 1, electrodes 13, matrix 14 and the output of the oscillator are connected as shown. The operator brings the rotating electrode 13 into contact with the upper surface of the matrix and moves it over the matrix surface at a predetermined speed to apply and fuse the electrode material to the matrix. Also, the continuous application of alternating signals generates considerable heat in the support or matrix, and in order to overcome this heat generation and avoid welding, the signals generated in the apparatus of the invention must be It turned out to be a half-wave signal that allowed heat to dissipate. Each material, both the matrix and the material to be applied, has special resistance properties. Thus, each change in one or both of these materials changes the resistance of the circuit. In FIG. 3, R ₁ = resistance of the electrodes R ₂ = resistance of the matrix and R ₃ = resistance of the circuits of 10 and 11. Changing R ₁ and R ₂ changes the frequency of the signal generated and the amplitude of that signal. As previously mentioned, a signal having an amplitude of 3 amps is believed to be the preferred amplitude. Above this amplitude decarbonization or combustion of the matrix occurs, and below this amplitude hydroxides form at the interface. FIG. 7 is a schematic diagram of an oscillator circuit used in the device according to the invention. In that circuit, a power supply 30 is connected across the input and a capacitor 31 is connected across the input. One side of the capacitor 31 is
It is connected via the LC circuit 32. The LC circuit 32 includes a variable inductance coil 33 and a capacitor 34 connected in parallel with the variable inductance coil 33. LC circuit 32 is connected to one side of the crystal oscillator circuit. The crystal oscillator circuit consists of an RC circuit composed of a crystal 35, an inductance 36, an NPN transistor 37, a variable resistor 38, and a capacitance 39. This oscillator circuit is connected to the output 50 via a capacitor 40 on one side and a diode 41 on the other side to generate a half wave signal across the output 50. In the actual equipment used, some components had the following properties: 31 = 1.2 furads 32 = 0.3 picofurads 33 = 0-25 millihenries 35 = 400-30kHz 36 = 20 millihenries 37 = NPN 38 = 3.5μ Farad 39 = 0 - 500 ohms 40 = 400μ Farad 41 = Diode To maintain the signal amplitude at 3 amps, R ₁
To change resistor 38 and change the frequency,
Change the inductance coil 33. C = capacitance and R ₁ of the circuit of Figure 3,
When R ₂ and R ₃ are the previously characterized resistances,
The optimal frequency F ₀ of the fused signal can be determined by: where L=R ₁ .R ₂ .R ₃ and C=capacitance of the circuit. L and C can be determined in a well-known manner. F ₀ depends on the materials being processed and applied, but ranges from 400Hz to 35MHz. It is believed that the frequency determines the speed of this method. To fuse the previously determined areas, measure their area. Since each discharge fuses approximately 0.3 ^mm2 , the moving speed can be determined by the following equation: : Moving speed = F ₁ ×0.3 × 60/mm/min/A Formula F ₁ = F ₀ /2 and A = Area to be covered (mm ² ) F ₁ is the number of discharges per second. As mentioned above, resistances R ₁ and R ₂ can be measured using known methods. However, measurements of resistance in the liquid phase were found to be unstable. In this case, the resistance is measured in a standard manner. Two electrodes, 1 cm apart and an area of 1 cm ² are placed in a bath of liquid phase, and the resistance is
Measurements were made with a delay of 20 seconds. After determining the variable parameters and connecting the apparatus, matrix and probes as shown in Figures 1 and 3,
The probe 13 is moved over the surface of the matrix in contact therewith at a predetermined speed. It is believed that rotation speed also affects the quality of the fusion. When the rotation speed is 5000rpm, the finish is uneven 200~300μ finish, and
The speed is assumed to be 10,000 rpm, and the finish is essentially a 15μ finish. The device of FIG. 2 operates in the same manner as the device of FIG. 1, and the method is essentially the same except that liquid electrodes are used instead of solid electrodes. In the specific examples below, the use of solutions in conjunction with the apparatus and in this method will be clearly understood. In each of these examples, the electrodes were connected such that when discharging, the electrodes were positively charged and the matrix was negatively charged, as will be apparent from the description. For fusing a second electrically conductive chemical element into a solid matrix of a first electrically conductive chemical element using solutions of a second electrically conductive chemical element, for each solution, the method involves the following steps at an ambient temperature of 20°C: It was carried out as follows. The metals of matrix 14 were connected into the circuit described above. The frequency was determined according to the above formula and the solution in container 17 was applied by moving the electrode over the surface of the first metal for varying periods of time determined by the formula. The electrodes were covered with cotton gauze or nylon to ensure uniform distribution of the second metal solution on the surface of the first metal. As is clear,
Other materials can be used. This arrangement also served to limit contamination of the solution when using graphite electrodes. They had a tendency to release graphite particles during movement. The treated samples were then sawed to form cross-sectional samples, washed in cold water, cleaned ultrasonically, embedded in plastic, ground, and polished to produce a flat surface and uniform edges. For other samples with soft metals that tend to lose edges when ground, two sections were clamped in face-to-face contact with the treated surfaces, embedded, ground, and polished as before. After embedding, the samples were etched with Nital for steel, ie, ferrous supports, and with Ammonium Hydrogen Peroxide for copper, ie, non-ferrous supports. During some applications, it may be necessary to adjust the frequency or application speed from time to time. These adjustments were due to changes in solution composition or matrix variations. Semi-quantitative electron probe microanalysis of the fused interface was performed using energy dispersive X-ray spectroscopy (Energy
Dispersive X-Ray Spectroscopy (EDX) and Scanning Electron Microscope (EDX)
It was carried out using Microscrpe (SEM). Place the surface of the embedded plastic approximately on top of it.
Conductivity was achieved by depositing a 20 μm carbon layer in a vacuum evaporator. This procedure was used to prevent charge build-up on the otherwise non-conducting material and subsequent instability of the SEM images. Carbon, which does not produce radiation detectable by EDX, was used in the presence of more conventional metallic coatings to prevent interference of such coatings with elemental analysis. The operating conditions of the SEM were chosen to minimize anomalous signals and continuous radiation while at the same time obtaining the best possible stereoscopic resolution. Conditions typically used for elemental analysis by EDX were as follows: Accelerating potential 10−20 kV Final aperture 200−300 Spot size 50 nm Beam current 100−300 pA Working distance 12−34 mm Magnification 5000−10000 Sample angle Perpendicular to the beam Take off angle 225° Count rate 800-2000cps Live time 60-80sec Energy calibration is AKd at 1.486keV
radiation and CuK radiation at 8.040 keV. A not-so-standard semi-quantitative analysis was applied to determine elemental concentrations and a guaranteed reference material (NBS478, 78%
Cu−24%Zn and NBS479a, Ni, 11%, Cr18
%, Fe) was used to verify the results. Multiple analyzes of reference materials were in excellent agreement with the guaranteed values from NBS. An average accuracy of ±1% was achieved. The size of the analyzed volume was calculated from Equation 1: pR(x) = 0.064 (E ₀ l ⁶⁸ − _{E c} l ⁶⁸ ) where R(x) is the mass range (X-ray production volume). p = density of the analyzed material E ₀ = accelerating potential E _c = critical excitation energy The diameter of the analyzed volume was calculated for typical analyzed elements and found to be: Ni 0.46 Cu 0.39 Fe 0.55 W 0.30 To evaluate the diffusion depth, a stationary beam was placed across the interface at a spacing greater than the aforementioned mass range. This ensured the accuracy of the analysis. Elemental concentration results were reported in weight percent for each measurement point across the fusion interface. As mentioned above, the metal solution disclosed in US Pat. No. 3,196,72 is new and forms the basis of the present invention. Broadly speaking, these solutions are aqueous solutions, have a PH of about 0.4 to 14, a resistance of 10 to 80 ohm cm, and contain the following components: (1) The metal to be fused to other metals Compounds of polyvalent metals that can be dissociated, compounds that can be complexed with (2) compounds, compounds (1) and
(2) is soluble in water or forms a water-soluble complex. (3) a stabilizer that functions to keep (1) and (2) and their complexes in solution; (4) a stabilizer that accelerates the reaction rate and reduces the valence of the polyvalent metal to a lower valency; A catalyst that has the function of catalyzing the complexing action between (1) and (2). acidic and/or
Alternatively, use an alkaline substance to ensure the appropriate pH for the usage conditions, and use metal compounds (1) and
It can also help keep (2) in solution. Some of these solutions may contain a sufficient amount of organic solvent to ensure dissolution of the metal and/or complex. Some other solutions require conductivity enhancers. And depending on the desired end result, brighteners can also be present. Wetting agents or surfactants can also be added. Various dissociable polyvalent metal compounds, usually metal salts or acids, can be used as component (1), as long as they are soluble in the aqueous medium. Typical compounds are: sodium molybdate, sodium tungstate, indium sulfate, nickel sulfate, nickel chloride, chloroauric acid, chromium trioxide, chromium sulfate, chromium chloride, cadmium chloride, Cadmium sulfate, stannous chloride, cobaltous sulfate, silver cyanide, silver nitrate. Typical ingredients (1) are based on the total weight of the solution:
It can be used in a range of 0.10 to 10% by weight. However, other amounts can be used, and the particular amount used depends on other conditions of use in a given case. Typical complexing agents useful as component (2) include pyrophosphate, ethylenediaminetetraacetic acid, citric acid, potassium iodide, and the like. Pyrophosphate also acts as a stabilizer. This component usually constitutes 3-10% by weight of the solution. However, this amount can vary and should be selected to give optimal complexation with (1). A wide variety of stabilizers and catalysts can be used as components (3) and (4), respectively. Typical stabilizers are: boric acid, citric acid, citrates, pyrophosphates, acetates and aluminum sulfate. On the other hand, suitable catalysts are:
Metal ions, such as iron, nickel, antimony and zinc ions, and organic compounds, such as dextrin, hydroquinone, gelatin,
Pepsin and gum acacia. The amounts of these ingredients can vary, but
Usually within the range of 0.01-0.5% by weight of each solution. A wide range of types can be used to obtain the desired PH value. Typical acids and bases are: Acids: sulfuric acid, hydrochloric acid, hydrofluoric acid, orthophosphoric acid, citric acid and oxalic acid. Bases: ammonium hydroxide, sodium hydroxide, potassium hydroxide and basic salts such as alkali carbonates and bicarbonates. Typical brighteners are formaldehyde and carbon disulfide. A surfactant or wetting agent used in some solutions is sodium lauryl sulfate. Other known ones can be used instead. In some solutions, conductivity enhancers such as sodium sulfate can be used. In the Examples and in the following, ferrous and ferric ions are added to the solution. Although the ions apparently migrated into the matrix at the same time as the molybdenum, there was no apparent material effect on the matrix or on the molybdenum fused with it. Molybdenum migration into the matrix was found to be enhanced by the presence of ferric and ferrous ions. Although the exact nature of this mechanism is unknown, it is believed that the presence of these ions forms a complex that increases the reduction of Mo ⁺⁶ to lower valence states. Certain other solutions require a second chemically conductive element to eliminate precipitation of the second element. These substances are, for example, citric acid, sodium pyrophosphate or ethyldiaminetetraacetic acid or equivalents thereof. Appropriate buffers are also added to certain solutions as necessary. Water is always deionized. Small amounts of brighteners such as formaldehyde, carbon disulfide, benzene, sulfuric acid or the like can be used in certain applications where an elegant appearance of the product is required. In these examples, unless otherwise specified,
The steel matrix was ASA1018 and the copper matrix was ASTM B-1333 alloy 110. EXAMPLE Atlas A151 1020 steel is connected as matrix 14 to the apparatus of FIG. 2 and a 10% solution of ammonium molybdate in water is placed in container 1
I put it in 7. The characteristics and processing conditions were as follows: Resistance of the matrix 0.0018 ohm Resistance of the probe 150 kohms Resistance of the circuit 0.01 ohm Frequency 650 Hz, 0.4 picofurads Contact area 2 cm ² Speed 60 cm/min Processing depth approximately 0.5 μm Deposition on the surface Approximately 15 μm Determined by measurement across 1 cm ² of plates with 1 cm spacing after a delay of 20 seconds. The samples of the examples were subjected to a hot corrosion test. 25% sulfuric acid was applied to the surface for 20 minutes at 325°C and there was no penetration of the surface. EXAMPLE An aqueous solution was prepared with the following formulation: Ingredients g/ sodium molybdate 37.8 Ammonium ferrous sulfate 7 Ammonium ferric sulfate 8.6 Citric acid 66.0 Water (distilled) 997 ml Sodium lauryl sulfate 0.5 Ammonium hydroxide to the required pH Amount Acacia (gum arabic) 0.1−0.2 Formaldehyde 7.5 ml The solution had the following properties: PH = 7.5 Resistance = 19 ohm cm Mo ⁺⁶ concentration = 1.8% by weight Fe ⁺² = 0.10% by weight Fe ⁺³ = ^{The 6} concentration of 0.10 wt% Mo ⁺ can vary from 1.5 wt% to 2.5 wt%, the PH can range from 7.2 to 8.2, and the resistance can range from 17 to 25 ohm cm. Reaction conditions Matrix: Copper Electrode: Graphite Electrode cover: Woven cotton Frequency: 9.09kHz Application speed: 736.2mm/min Application time: 2 minutes In the solutions described in Examples and , ferrous and ferric ions , is believed to be the action of reducing the Mo ⁺⁶ valence state to a lower valence state. Although the ions are apparently transported simultaneously as shown in FIG. 6, it is clear that they do not substantially affect the properties of the matrix or molybdenum. When this sample is examined under an optical microscope, there is a dark silver continuous molybdenum coating without pits. Table below and Figure 6, SEM/Across the interface between matrix and applied metal.
As shown in the EPMA scan, the molybdenum is fused to a depth of at least 4 μm and the surface precipitation is approximately 1 μm.
It turns out that m.

[Table] Example An aqueous solution with the same formulation as in Example was prepared and applied under the following conditions: Reaction conditions Matrix: Steel (ASA1018) Electrode: Graphite Electrode cover: Woven cotton Frequency: 4.11kHz Application speed: 739.8mm /min Application time: 3 minutes When scanned with an optical microscope, a continuous dark silver surface was present. The photomicrograph of FIG. 7 shows the deposition of a 1 micron thick substantially uniform layer of uniform density molybdenum. Figure 8, SEM/EPMA scan across the interface between the support and the applied metal shows that molybdenum was present at a depth of at least 10 microns, and the molybdenum gradient is listed in the table below. That's right.

【table】

[Table] Example An aqueous solution with the following formulation was prepared: Ingredients g/ sodium tungstate 31.40 Ammonium ferric sulfate 8.63 Ferrous sulfate 4.98 Citric acid 66.00 Water (distilled) 1000ml Ammonium hydroxide Amount to achieve required pH Sodium lauryl sulfate 0.1 Formaldehyde 5ml This solution had the following properties: PH = 7.99 Resistance = 22 ohm cm W ⁺⁶ concentration = 1.75% by weight Fe ⁺² = 0.1% by weight Fe ⁺³ = 0.1% by weight The concentration of W ⁺⁶ is The PH can vary between 1.6 and 2.5%, the PH between 7.5 and 8.5 and the resistance between 18 and 24 ohm cm, respectively. Reaction conditions Matrix: Copper Electrode: Graphite Cover: Cotton gauze Frequency: 3.83kHz Application speed: 689.4mm/min Application time: 3 minutes As shown in the micrographs in Figures 9 and 10, the sample has a thickness of approximately 1 It showed a uniform deposit of micron tungsten. SEM/EPMA scanning is
As can be seen from the table below and FIG. 11, tungsten fusion into copper was demonstrated to a depth of at least 5.0 microns.

[Table] Example An aqueous solution having the following formulation was prepared. Ingredients g/ Sodium tungstate 34.00 Ferrous sulfate 4.98 Ferrous ammonium sulfate 7.02 Ferric ammonium sulfate 8.62 Citric acid 66.00 Water (distilled) 980ml Ammonium hydroxide Amount to reach required pH Sodium lauryl sulfate 0.10 Note 1 or 2 can be used can. This solution had the following properties: PH = 8 Resistance = 20.9 ohm cm W ⁺⁶ = 1.9 wt% Fe ⁺² = 0.1 wt% Fe ⁺³ = 0.1 wt% Tungsten concentration was 1.6-2.5 wt% Between, PH
can vary between 7.5 and 8.5, and conductivity between 18.8 and 22.8 ohm cm, respectively. Reaction conditions Matrix = Copper (ASA1018) Electrode = Graphite Electrode cover = Cotton gauze Frequency = 4.78 Application speed = 860.4 mm/min Application time = 3 minutes Figure 12, which is an examination of this sample by SEM/EPMA, shows approximately 0.5 μm 13 and the table below, tungsten is deposited at a depth of at least 3 μm.

[Table] Example An aqueous solution with the following formulation was prepared: Ingredients /g/ Indium sulfate 40.0 Aluminum sulfate 9.6 Sodium sulfate 3.5 Gelatin 0.05−0.1 Sodium lauryl sulfate 0.1−0.2 Water (distilled) 1000 ml This solution had the following properties. were: PH = 1.60 Resistance = 51.8 ohm cm Concentration ⁺³ = 1.75% by weight Concentration Al ⁺³ = 0.077% by weight The concentration of indium is between 0.2 and 2.2%, and the PH is between 1.60 and 2.2%.
1.68 and the resistance can vary between 48.8 and 54.8 ohm cm respectively. Reaction Conditions Matrix = Copper Electrode = Graphite Electrode Cover = Cotton Gauze Frequency = 4.75 Application Speed = 855 mm/min Application Time = 3 minutes Examination of this sample with an optical microscope and a scanning electron microscope revealed structural differences as shown in Figure 14. A continuous surface without defects is shown. Table below and Figure 15 and SEM/EPMA across the interface between the copper matrix and the indium layer.
As can be seen, there were approximately 1 μm of precipitates and indium amalgamation to a depth of at least 4 μm.

[Table] Example The deep liquid of the example was used and applied to a steel matrix: Reaction conditions Matrix = Copper (ASA1010) Electrode = Platinum Electrode cover = Nylon fabric Frequency = 6.29kHz Application speed = 1132.2mm/min Application Time = 3 minutes A uniform continuous layer of indium approximately 1 μm thick was deposited on the surface of the matrix, as shown in FIGS. 16 and 17. SEM across the interface/
The EPMA scan, Figure 16 and table below showed fusion to a depth of at least 3 μm.

[Table] Figure 18 shows a solid precipitate of nickel with a uniform density and a thickness of approximately 1.5 μm. Table below and No. 19
As seen from the SEM/EPMA scan across the interface between the matrix and the nickel layer,
The nickel fused to a depth of at least 4 μm. Depth μm Element weight % 1 Ni 92.6 2 Ni 4.5 3 Ni 3.3 4 Ni 1.0 Example An aqueous solution with the following formulation was prepared: Ingredients g/ nickel sulfate 24.89 nickel chloride 37.3 boric acid 24.9 formaldehyde 3 ml/benzenesulfone Acid 10ml/ Sodium Lauryl Sulfate 0.1 Water (distilled) 900 This solution had the following properties: PH = 3.10 Resistance = 22.5 ohm cm Concentration of Ni ⁺² = 6% by weight Nickel concentration between 2 and 10%; PH is 3.10~
3.50, and the resistance can vary between 17 and 26 ohm cm. Reaction Conditions Matrix = Copper Electrode = Graphite Electrode Cover = Cotton Gauze Frequency = 7.50kHz Application Speed = 1350mm/min Application Time = 3 minutes Example A solution identical to the recipe for Example X was prepared;
And applied to steel matrix: Reaction conditions Matrix = Copper (ASA1018) Electrode = Graphite Electrode cover = Cotton gauze Frequency = 7.50kHz Application speed = 1350mm/min Application time = 3 minutes As shown in Figure 20, the nickel layer was It is continuous and has a substantially uniform thickness of about 1.2 μm. As shown in FIG. 21 and the table below, it can be seen that the nickel is fused to a depth of at least 3 μm. Depth μm Element concentration (wt%) 1 Ni 95.9 2 Ni 28.0 3 Ni 0.7 Example An aqueous solution with the following formulation was prepared: Component g/ chloroplatinic acid 2.5 Potassium ferrocyanide 15.0 Potassium carbonate 15.0 Water (distilled) 1000 ml of this solution had the following properties: PH = 10.99 Resistance = 40 ohm cm Concentration = 0.14 wt% PH was between 3.70 and 11, and the concentration of Au ⁺³ ions was between 0.1 and 0.5
weight percent, and resistance can vary between 40 and 72 ohm cm, respectively. Reaction conditions Matrix = Copper Electrode = Platinum Electrode cover = Cotton gauze Frequency = 4.33KHz Application speed = 779.4mm/min Application time = 2 minutes Gold deposited surface approximately 1.5μm thick when observed with optical and scanning electron microscopy It became clear. The deposits are continuous and uniformly dense as shown in FIG. SEM/EPMA scans across the interface showed fusion of gold to a depth of at least 3 μm, as shown in the table below and in Figure 23. Depth μm Element concentration (wt%) 0.5 Au 61.3 1.0 Au 9.6 2.0 Au 0.9 3.0 Au 0.5 Example XI An aqueous solution with the same formulation as Example X was prepared: Reaction conditions Matrix = Copper Electrode = Graphite Electrode cover = Cotton gauze Frequency = 3.95 KHz Application speed = 711.0 mm/min Application time = 2.0 min Observations using optical and scanning electron microscopy revealed gold surface deposits approximately 1.0 μm in size. The precipitate had uniform thickness and density, as shown in FIG. SEM/EPMA scans across the interface showed fusion of gold to a depth of at least 4.0 μm, as shown in the table below and FIG. Depth μm Element concentration (wt%) 0.5 Au 84.9 1.5 Au 10.6 2.0 Au 2.1 3.0 Au 0.8 4.0 Au 0.6 Example XII An aqueous solution with the following formulation was prepared: Component g/ Chromium trioxide 1.50 Chromium sulfate 0.06 Sodium silico fluoride 0.2 (Sodium Silico Fluoride) Carbon disulfide 2-3 ml Sodium lauryl sulfate 0.05 Water (distilled) Amount to make 1000 ml This solution had the following properties: PH = 0.6 Resistance = 12 ohm cm Concentration of Cr ⁺⁶ = 7.8 wt% PH can vary between 0.6 and 1.0, the concentration of Cr ⁺⁶ ions between 3 and 20 wt%, and the resistance between 11 and 14 ohm cm. Reaction conditions Matrix = Copper Electrode = Graphite Electrode cover = Cotton gauze Frequency = 6.25KHz Application speed = 1125mm/min Application time = 5.0min Observation by optical microscope and scanning electron microscope shows that the surface of chromium with a thickness of approximately 1 μm is deposited. revealed. Although the surface of the layer was irregular, the deposits were defect-free and continuous as shown in FIG. SEM/EPMA scans across the interface showed chromium fusion to a depth of at least 3.0 μm, as shown in the table below and FIG. Depth μm Element concentration (wt%) 0.5 Cr 94.0 1.0 Cr 32.0 2.0 Cr 1.8 3.0 Cr 1.0 Example An aqueous solution with the same formulation as used in Example XII was prepared: Reaction conditions Matrix = Copper (ASA1018) Electrode = Graph Eye Electrode Cover = Cotton Gauze Frequency = 6.48 kHz Application Speed = 1166.4 mm/min Application Time = 5.0 min Observations by optical and scanning electron microscopy revealed surface deposits of chromium approximately 3.0 μm thick. This is shown in FIG. SEM/EPMA scans across the interface showed chromium fusion to a depth of at least 5.0, as shown in the table below and Figure 29. Depth μm Element concentration (wt%) 1.0 Cr 100 2.0 Cr 97.2 3.0 Cr 20.8 4.0 Cr 2.5 5.0 Cr 2.1 Example An aqueous solution with the following formulation was prepared: Component g/ Chromic chloride 213 Sodium chloride 36 Ammonium chloride 26 Boron Acids 20 Dimethylformamide 400 ml Sodium acetate 3.0 Sodium lauryl sulfate 0.5 Water (distilled) Amount to make 1000 ml This solution had the following properties: PH = 3.0 Resistance = 17.4 ohm cm Concentration of Cr ⁺³ = 2.5-3.5 PH is The concentration of Cr ⁺³ can vary between 18. and 5% by weight, and the resistance between 16 and 20 ohm cm, respectively. Reaction conditions Matrix = Copper Electrode = Graphite Electrode cover = Cotton gauze Frequency = 6.85KHz Application speed = 1251mm/min Application time = 3.0min Observations using an optical microscope and a scanning electron microscope show that the surface structure of a chromium film with a thickness of approximately 0.5μm is revealed the outcome. This precipitate was substantial and continuous, as shown in FIGS. 30 and 31. SEM/EPMA scans across the interface showed chromium fusion to a depth of at least 3.0 μm, as shown in the table below and Figure 32. Depth μm Element concentration (wt%) 1 Cr 21.2 2 Cr 4.0 3 Cr 0.9 Example An aqueous solution with the same formulation as that prepared in the example was used: Reaction conditions Matrix = Copper (ASA1018) Electrode = Graphite Electrode cover = Cotton gauze Frequency = 6.85 KHz Application speed = 1251 mm/min Application time = 3.0 min Observation by optical and electron microscopy revealed surface deposits of chromium approximately 1.0 μm thick. Although the surface of the precipitate was slightly irregular, the precipitate was solid and free of defects, as shown in Figures 33 and 33A. SEM/EPMA scans across the interface showed fusion at least 3.0 μm deep, as shown in the table below and FIG. Depth μm Element concentration (wt%) 0.5 Cr 97.2 1.0 Cr 97.6 1.5 Cr 22.2 2.0 Cr 1.5 3.0 Cr 0.8 Example An aqueous solution of the following formulation was prepared: Component g/ cadmium chloride 6.74 Tetrasodium pyrophosphate 54 Water (distilled) 1000ml This solution had the following properties: PH = 10 Resistance = 33 ohm cm Concentration of Cd ⁺² = 0.32% by weight PH was between 10 and 10.2, and concentration of Cd ⁺² ions was between 0.2 and 0.5
weight percent, and the resistance can vary between 28 and 35 ohm cm, respectively. Reaction conditions Matrix = Copper Electrode = Graphite Electrode cover = Cotton gauze Frequency = (1) 7.29kHz; (2) 7.91kHz Application speed = (1) 1312.2mm/min; (2) 1423.8mm/min Application time = (1) ) 1.0 min; (2) 3.0 min In this example, the solutions used were as initially described above and were applied according to the conditions given in (1). The second solution described in Example XX is
It was then applied under the conditions shown in (2). Observation using optical microscopy and scanning electron microscopy revealed surface deposits of cadmium approximately 4 μm thick. This precipitate is not homogeneous as shown in Figure 35, but it crosses the interface.
SEM/EPMA scans showed cadmium coalescence at least 9 μm deep, as shown in the table below and in FIG. Depth μm Element concentration (wt%) 2 Cd 77.4 3 Cd 65.2 4 Cd 6.7 5 Cd 1.2 6 Cd 0.48 7 Cd 2.1 8 Cd 2.9 9 Cd 0.89 Example An aqueous solution of the following formulation was prepared: Component g/ Cd 26.65 Sodium chloride 8.7 Boric acid 15.0 Aluminum sulfate 17.5 Acacia (gum arabic) 0.25 Sodium tetraborate 5.0 Benzene sulfonic acid 2.5 Sodium lauryl sulfate 0.5 Water (distilled) 1000 ml This solution had the following properties: PH = 3.40 Resistance = 54 ohms Concentration of Cd ⁺² in cm = 1.1% PH can vary between 3.2 and 3.5, concentration of Cd ⁺² ions between 1 and 4% by weight, and resistance between 45 and 55 ohm cm. Reaction conditions Matrix = Copper Electrode = Platinum Electrode cover = Nylon cloth Frequency = 13.7kHz Application speed = 2466mm/min Application time = 2 minutes Observations using an optical microscope and a scanning electron microscope revealed that cadmium surface deposits with a thickness of approximately 1 μm were observed. Although the surface of the precipitate was irregular, it was solid and continuous as seen in Figure 37. SEM/EPMA scans across the interface are shown in the table below and in Figure 38. As shown in the figure, it showed fusion of cadmium with a depth of at least 4 μm.Depth μm Element concentration (wt%) 0.5 Cd 73.3 1.0 Cd 8.8 2.0 Cd 1.4 3.0 Cd 1.2 4.0 Cd 1.1 Example Aqueous solution of following formulation Prepared: Ingredients g/ Stannous chloride 77.3 Sodium hydroxide 66.0 Sodium acetate 14.7 Water (distilled) 1000 ml This solution had the following properties: PH = 1.24 Resistance = 8.6 ohm cm Concentration of Sn ⁺² ions = 4% by weight PH is between 11.2 and 12.7, Sn ⁺² ion concentration is between 2 and 5
Weight % and resistance can vary between 6.2 and 10.3 ohm cm, respectively. Reaction conditions Matrix = Copper Electrode = Graphite Electrode cover = Cotton gauze Frequency = 9.85KHz Application speed = 1773mm/min Application time = 2 minutes Observations using an optical microscope and a scanning electron microscope revealed that the surface deposits were approximately 1.2 μm thick. was revealed. The precipitate had uniform thickness and was homogeneous. This is shown in FIG. SEM/EPMA scans across the interface showed tin fusion at least 4 μm deep, as shown in the table below and in FIG. Depth μm Element Concentration (wt%) 1 Sn 91.4 2 Sn 4.4 3 Sn 0.9 4 Sn 0.5 Example A solution with the following formulation was prepared: Component g/ Stannous chloride 9.4 Tetrasodium pyrophosphate 44.7 Dextrin 6.25 Water (distilled) ) 1000ml Sodium Lauryl Sulfate 0.5 This solution had the following properties: PH = 9.05 Resistance = 34 ohm cm Concentration of Sn ⁺² = 0.50% by weight PH between 9 and 9.7, concentration of Sn ⁺² ions 0.4 ~1% by weight, and the resistance can vary between 30 and 36 ohm cm, respectively. Reaction conditions Matrix = Copper Electrode = Graphite Electrode cover = Cotton gauze Frequency = 9.85 kHz Application speed = 1773 mm/min Application time = 2 minutes Observations using an optical microscope and a scanning electron microscope revealed that the tin surface deposits were approximately 4 μm thick. was revealed. This deposit consists of a bottom uniform, substantially homogeneous layer approximately 1 μm thick and an outer slightly porous layer approximately 3 μm thick, as shown in FIG. appear. SEM/EPMA scans across the interface showed tin amalgamation at least 5 μm deep, as shown in the table below and in FIG. Depth μm Element concentration (wt%) 1 Sn 97 2 Sn 97.3 3 Sn 94.3 5 Sn 1.0 Example The same aqueous solution as prepared in the example was used: Reaction conditions Matrix = Copper (ASA1010) Electrode = Graphite Electrode cover =Cotton gauze Frequency = 10.61 kHz Application speed = 1909.8 mm/min Application time = 3 minutes Observation with an optical microscope and a scanning electron microscope revealed surface deposits of tin with a thickness exceeding 2 μm. This layer, as shown in Figure 43,
Porous but continuous ivy. SEM/EPMA scans across the interface showed tin amalgamation at least 2 μm deep, as shown in the table below and in Figure 44. Depth μm Element concentration (wt%) 0.5 Sn 96.2 1.0 Sn 81.4 2.0 Sn 2.5 Example XI An aqueous solution with the following formulation was prepared: Component g/ Cobaltous Sulfate 252 Sodium Fluoride 14 Boric Acid 45 Dextrose 5 Sodium Lauryl Sulfate 0.2 1000 ml of water (distilled) This solution had the following properties: PH = 6.03 Resistance = 28.5 ohm cm Concentration of Co ⁺² = 5.3% by weight PH was between 4.5 and 6.5, concentration of Co ⁺² ions was 2 ~6% by weight and the resistance can vary between 25 and 30 ohm cm. Reaction conditions Matrix = Copper Electrode = Platinum Electrode cover = Nylon mesh Frequency = 5.1 kHz Application speed = 918 mm/min Application time = 3.0 minutes Observations using an optical microscope and a scanning electron microscope revealed that the surface fracture of a cobalt film with a thickness of approximately 6.5 μm was observed using an optical microscope and a scanning electron microscope. The product was revealed. This layer was uniform and continuous, as shown in Figure 45. SEM/EPMA scans across the interface showed cobalt amalgamation at least 20 μm deep, as shown in the table below and FIG. Depth μm Element Concentration (wt%) 10 Co 2.65 15 Co 1.6 20 Co 0.87 25 Co 0.44 Visual inspection and previous experiments revealed that cobalt deposits above the 10 μm level are extremely dense. Ta. Example XII An aqueous solution of the following formulation was prepared: Component g/ Silver cyanide 26 Potassium cyanide 46 Potassium carbonate 37 Sodium lauryl sulfate 1 Carbon disulfide 1-2 Water (distilled) 1000 ml This solution had the following properties: PH = 11.55 Resistance = 10.5 ohm cm Ag ⁺¹ concentration = 2.09 wt% PH is between 11.2 and 11.7, concentration of Ag ⁺¹ ions is between 1 and 3
The weight percent and resistance could be varied between 8 and 13 ohms, respectively. Reaction conditions Matrix = Copper Electrode = Platinum Electrode cover = Nylon Frequency = 7.7KHz Application speed = 1386mm/min Application time = 1.0min Observations using an optical microscope and a scanning electron microscope revealed that a silver surface precipitate with a thickness of approximately 5 μm was observed. revealed. The structure is shown in Figures 47 and 47A. SEM/EPMA scans across the interface should be performed at least 3 times as shown in the table below and in Figure 48.
It showed fusion of silver with a depth of μm. Depth μm Element concentration (wt%) 1 Ag 98.7 2 Ag 91.4 3 Ag 46.3 4 Ag 2.4 5 Ag 1.0 Example An aqueous solution with the following formulation was prepared: Component g/ Silver nitrate 29 Potassium iodide 398 Citric acid 6 Dextrose 5 Two Carbon sulphide 1.5 Ammonium hydroxide Quantity for required PH Water (distilled) 1000 ml This solution had the following properties: PH = 5.6 Resistance = 6.6 ohm cm Ag ⁺¹ concentration = 1.84% by weight PH between 1.5 and 2 , the concentration of Ag ⁺¹ ions is 0.5-2.5
% by weight and the resistance can vary between 6 and 12 ohm cm, respectively. Reaction conditions Matrix = Copper Electrode = Graphite Electrode cover = Cotton gauze Frequency = 9.5KHz Application speed = 1710mm/min Application time = 2.0min Observation by optical microscope and scanning electron microscope shows that the surface of silver with a thickness of approximately 2 μm is deposited. revealed. Its structure is shown in FIG. SEM/EPMA scans across the interface showed silver fusion at least 2.00 μm deep, as shown in the table below and in FIG. Depth μm Element concentration (wt%) 1 Ag 97.7 2 Ag 97.5 3 Ag 28.0 4 Ag 3.8 5 Ag 2.8 6 Ag 1.0 From the above examples, it can be seen that the second metal and the first metal in the solution pass through the medium of these solutions. It turns out that it can fuse with metal.

[Brief explanation of the drawing]

FIG. 1 is a schematic perspective view of one embodiment of a device according to the invention for use in accordance with the method of the invention. FIG. 2 is a schematic perspective view of a second embodiment of the device according to the invention for use in accordance with the method of the invention. FIG. 3 is a schematic electrical circuit used in the present invention. FIG. 4 is a circuit diagram of an oscillator used in an apparatus according to one embodiment of the invention.
FIG. 5 is a composite SEM micrograph of the right and left halves of a copper matrix fused with molybdenum with a molybdenum solution using the method of the present invention. The left half is a 1250× magnification and the right half is an 8× magnification of the marked area of the left half. 6th
The figure shows SEM/EPMA across the sample shown in Figure 5.
Figure 2 is a graph of a scan and shows the fusion of molybdenum and copper. FIG. 7 is a composite SEM micrograph of the right and left halves of a steel matrix fused with molybdenum in a molybdenum solution using the method of the present invention. The left half is a 1250× magnification and the right half is an 8× magnification of the marked area of the left half. Figure 8 crosses the sample shown in Figure 7.
Figure 2 is a graph of a SEM/EPMA scan and shows the fusion of molybdenum and copper. FIG. 9 is a composite micrograph of the right and left halves of a copper matrix fused with tungsten in a tungsten solution using the method of the present invention. The left half is a 1250× magnification and the right half is an 8× magnification of the marked area of the left half. FIG. 10 is another SEM micrograph of the sample of FIG. 9 at 10,000× magnification of the area marked in FIG. 11th
The figure crosses the samples shown in Figures 9 and 10.
2 is a graph of a SEM/EPMA scan. FIG. 12 is a composite micrograph of the right and left halves of a steel matrix fused with tungsten in a tungsten solution using the method of the present invention. The left half is 1310×
, and the right half is an 8× magnification of the marked area of the left half. FIG. 13 is a graph of a SEM/EPMA scan across the sample shown in FIG. 12 and shows fusion of tungsten and steel. FIG. 14 is a composite micrograph of the right and left halves of a copper matrix fused with indium using an indium solution using the method of the present invention.
The left half is a 1250× magnification and the right half is an 8× magnification of the marked area of the left half.
FIG. 15 is a graph of an electron microprobe scan across the sample shown in FIG. FIG. 16 is a composite SEM micrograph of the right and left halves of a steel matrix fused with indium using an indium solution using the method of the present invention. The left half is 625
× magnification, and the right half is an 8× magnification of the marked area in the left half. Figure 17 shows
17 is a graph of a SEM/EPMA scan across the sample shown in FIG. 16; FIG. 18 is a composite SEM micrograph of the right and left halves of a copper matrix fused with nickel in a nickel solution using the method of the present invention. The left half is a 1250× magnification and the right half is an 8× magnification of the marked area of the left half. FIG. 19 is a graph of a SEM/EPMA scan across the sample shown in FIG. 20th
The figure is a composite SEM micrograph of the right and left halves of a steel matrix fused with nickel in a nickel solution using the method of the invention. The left half is 1310
× magnification, and the right half is an 8× magnification of the marked area in the left half. Figure 21 shows
21 is a graph of a SEM/EPMA scan across the sample shown in FIG. 20; FIG. Figure 22 is a composite SEM micrograph of the right and left halves of a copper matrix fused with gold. The left half has a magnification of 1310×, and the right half has an 8× magnification of the marked area of the left half.
It is an expansion of FIG. 23 is a graph of a SEM/EPMA scan across the sample shown in FIG. 22 and shows gold fused into the copper matrix. Second
Figure 4 shows a composite of the right and left halves of a steel matrix fused with gold using a gold solution using the method of the present invention.
This is a SEM micrograph. The left half is a 1310× magnification and the right half is an 8× magnification of the marked area of the left half. FIG. 25 is a graph of a SEM/EPMA scan across the sample shown in FIG. 23 and shows fused gold in the steel matrix. FIG. 26 shows a copper matrix fused with chromium with a first chromium solution using the method of the present invention.
This is a SEM micrograph at a magnification of 10,000×. 27th
The figure shows the SEM/SEM across the sample shown in Figure 26.
Figure 2 is a graph of an EPMA scan and shows the fusion of chromium and copper. FIG. 28 is a SEM micrograph at 10,000× magnification of a steel matrix fused with chromium using the method of the present invention with the first chromium solution described above. FIG. 29 is a graph of a SEM/EPMA scan across the sample shown in FIG. 28 and shows fusion of chromium and steel. Figure 30 shows a composite of the right and left halves of a copper matrix fused with chromium with a secondary chromium solution using the method of the present invention.
This is a SEM micrograph. The left half is a 625× magnification and the right half is an 8× magnification of the marked area of the left half. Figure 31 is a further enlargement of the enlarged area of Figure 30 at a magnification of 10000x.
This is a SEM micrograph. FIG. 32 is a graph of a SEM/EPMA scan across the sample shown in FIG. 30 and shows fusion of chromium and copper. Third
Figure 3 is a composite SEM micrograph of the right and left halves of a steel matrix in which chromium was fused with a secondary chromium solution using the method of the present invention. The left half
The magnification is 1250×, and the right half is an 8× magnification of the marked area of the left half. 33rd A
The figure is a further magnified SEM micrograph of the enlarged area of Figure 33 at 10000x magnification. Figure 34 shows SEM/EPMA across the sample shown in Figure 32.
Graph of a scan and showing the fusion of chrome and steel. FIG. 35 shows the first method using the method of the present invention.
This is a composite micrograph of the right and left halves of a copper matrix fused with cadmium using a cadmium solution. The left half is a 1310× magnification and the right half is a 5× magnification of the marked area of the left half. Figure 36 crosses the sample shown in Figure 35.
Figure 3 is a graph of a SEM/EPMA scan showing the fusion of cadmium and copper. FIG. 37 is a photomicrograph at 11500x of a steel matrix fused with cadmium with a second cadmium solution using the method of the present invention. Figure 38 crosses the sample shown in Figure 37.
Figure 2 is a graph of a SEM/EPMA scan and shows the fusion of cadmium and steel. FIG. 39 is a composite micrograph of the right and left halves of a copper matrix fused with tin with a stannous solution using the method of the present invention. The left half is a 655× magnification and the right half is an 8× magnification of the marked area of the left half. FIG. 40 is a SEM/EPMA scan across the sample shown in FIG. 39 and shows melting of tin and copper. FIG. 41 is a composite micrograph of the right and left halves of a copper matrix fused with tin with a stannic solution using the method of the present invention.
The left half is a 326× magnification and the right half is an 8× magnification of the marked area of the left half.
Figure 42 crosses the sample shown in Figure 41.
SEM/EPMA scan and shows fusion of tin and copper. FIG. 43 shows that using the method of the present invention,
Composite SEM micrographs of the right and left halves of a steel matrix fused with tin in a stannic solution. The left half is a 1310× magnification and the right half is an 8× magnification of the marked area of the left half. Figure 44 crosses the sample shown in Figure 43.
SEM/EPMA scan and shows the fusion of tin and steel. FIG. 45 shows that using the method of the present invention,
SEM micrograph at 5200× magnification of a copper matrix fused with cobalt in a cobalt solution. Figure 46 crosses the sample shown in Figure 45.
SEM/EPMA scan and shows fusion of cobalt and copper. Figures 47 and 47A are micrographs of copper matrices fused with silver in a ferrous silver solution using the method of the present invention. Figure 47 shows
The left half is a composite photograph with 625× magnification and the right half is an 8× magnification of the marked area of the left half. Figure 47A is a further magnified SEM micrograph of the enlarged area of Figure 47 at 10,000x magnification. Figure 48 is a SEM/EPMA scan across the sample shown in Figure 47 and shows fusion of silver and copper. FIG. 49 is a SEM micrograph at 10,000× magnification of a copper matrix fused with silver with a ferric silver solution using the method of the present invention. Figure 50 shows the SEM/SEM across the sample shown in Figure 49.
Figure 2 is a graph of an EPMA scan and shows the fusion of silver and copper. 10... Power supply, 11... Oscillator, 12...
...Holder, 13... Electrode, probe, 14...
matrix or support, 15...clamp,
16...Line, 17...Container, 18...Pipe, 1
9... Electrode, 20... Insulated handle, 21... Main channel, 22... Side channel, 23...
Valve, 30... Power supply, 31... Capacitor,
32...LC circuit, 33...Variable inductance coil, 34...Capacitor, 35...Crystal, 3
6...Inductance, 37...NPN transistor, 38...Variable resistor, 39...Capacitance, 40...Capacitor, 41...Diode, 50...Output.

Claims (1)

Claims: 1. A solution used to fuse a second metal into a matrix of a first metal, comprising: a first metal containing said second metal in a dissociable multivalent form;
0.10 to 10% by weight of a compound, and a second compound capable of forming a complex with the first compound.
0.30 to 10% by weight of the first compound and the second compound.
the compounds are either water-soluble or water-soluble complex-forming; 0.1 to 0.5% by weight of a stabilizer to keep the first compound, the second compound and their complexes in solution; and the reaction rate. of the second metal, reducing the valence of the polyvalent form of the second metal to a lower valence;
consisting essentially of 0.1 to 0.5% by weight of a catalyst that catalyzes the complexing action between the compound and said second compound, and the balance consisting of a solvent selected from water, an organic solvent or a mixture thereof, and at room temperature A solution with a resistance of 80Ωcm.