DD202312A5 - PROCESS FOR MELTING - Google Patents

Abstract

A method of fusing a second conductive member to the matrix of a first conductive member is provided by contacting the second member in the form of a dissociable solution with the first conductive member and subjecting it to a chopped electrical signal of a particular frequency , Solutions for carrying out the process are set forth and products produced by the process.

Description

Verschmelzungaverfahren

Field of application of the invention

The invention relates to fusion processes, plants for carrying out such processes and products from such processes, as well as solutions for use in the process.

This application is a divisional treatment of U.S. Patent No. 224,762, filed January 13, 1981.

For the purposes of this application, the term "fusion" is intended to mean a process by which various elements are chemically or physically linked. "

Characteristic of the known technical solutions; So far, it has been customary to treat substrates or matrices in various ways to improve the characteristics of the matrix for a particular application. Sometimes in these treatments, the matrix was considered a body and in other techniques only the surface characteristics were increased.

However, these techniques had limitations. The workpiece or matrix may have a certain shape which does not lend itself to a particular characteristic increasing process; by the method already existing desired properties of the workpiece can be destroyed; or the treated workpiece, although having certain improved characteristics, may have other reduced properties.

In general, the method used depends on the workpiece to be treated or the matrix to be treated and the desired properties. More specifically, coating techniques, heat treatment, anodization, arc spraying, vacuum evaporation, chemical deposition, sputtering, and ion plating are all common processes.

Non-ferrous metals can be hardened by aging, heat treatment or anodizing.

However, these techniques do not provide adequate protection against dry abrasion wear.

By. Spray coating techniques could not improve the corrosion resistance or physical properties of ferrous materials *

The abrasion resistance of non-iron substrates could be improved by electrochemical or electromechanical plating with hard chrome, but this measure is expensive and time consuming.

The other techniques, such as arc spraying, vacuum evaporation and sputtering, also have disadvantages because the deposited layer is usually thin, the interfacial bonding strength is poor, or it can only be used to treat small surface areas.

In practice, the disadvantages are that guest techniques or high voltages are required, which cause difficulties and limit their versatility,

For ease of reference, in this specification the term "first conductive chemical element" shall refer to the matrix with which the fusion is to occur; and the term "chemical element" is intended to indicate such element or an alloy thereof; the term "second conductive chemical element or an alloy thereof" is intended to indicate the element to be fused to the matrix.

It is also intended that the term "fusion" used in this specification is intended to mean penetration of atoms or molecules of a second element into the solid matrix of a first element or alloy thereof.

Aim of the invention;

The invention is therefore based on the object of at least partially eliminating these disadvantages by providing a novel method and apparatus for fusing the most diverse conductive elements with either ferrous or non-ferrous dies.

Another object of the invention relates to a novel An **

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and a method using a deposition technique at ambient temperatures that achieves high bond strength without distortion or loss of workpiece or die characteristics.

Another object of the invention relates to a method in which the use of process gas-air is not required and in which no security risks occur and caused by the no heat distortion *

High object of the invention relates to a method that requires a low energy consumption and the coating material is still effectively applied.

Another object of the invention is to provide a system that is cheap and portable and lightweight. One of the objects of the invention relates to a process which provides a solid interfacial bond, and which requires no skilled worker to perform it. "

Another object of the invention is to provide solutions of conductive chemical elements that can be used for the fusion of these chemical elements with solid matrices of other conductive elements or alloys thereof.

It is also an object of the invention to produce new and improved products which will have improved physical and chemical properties.

Explanation of the essence of the invention:

According to the invention, there is provided a method, a plant and solutions for changing the surface properties of a metal or alloy thereof at ambient temperatures by physically applying a second conductive chemical element to the surface whose characteristics are to be changed and applying of a chopped electrical signal of a given frequency to both elements when the physical contact has to be used »

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Ea is a plant gaff chaff s, which is a Schviingkreia for generating a Haibwellensignals at the output and means for the connection of a second element to be melted, and the first chemical element, with daa the second is to be merged with the output ·

Solutions are also provided for use in the process and in connection with the plant. These solutions consist of a solution of a conductive chemical of the chemical to be fused in a dissociable form, which may be present in an amount of 0.10 to 10 mass and has a pH ranging from 0.4 to 14. It is favorable if the resistivity of the solution is in the range of 5 to 500 ohm-cm, preferably between 10 and 80 ohm-cm.

By applying the method to ferrous and non-ferrous egg matrices, new products are produced in which a second chemical conductive element has been fused into a first chemical conductive element to a depth greater than 0.5 μm and a surface layer of the second chemical conductive Element has been applied in thicknesses of more than 0,5 / um «

Embodiments?

These and other objects and features of the invention will become more apparent from the following description and drawings, in which apexical examples of the process plant and of products of the process for illustrating the invention are explained.

In the drawings:

1 is a general perspective view of an embodiment of the plant according to the invention, which is used for the inventive method}

Fig. 2 is a general perspective view of a second embodiment of the plant according to the invention, which is used for the inventive method;

3 shows a schematic electrical circuit for the Er-

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findang;

Fig. 4 is a circuit diagram of an oscillator used for the plant in an embodiment of the invention;

Fig. 5 is a photomicrograph at 5O0 magnification of a steel sample treated with titanium monocarbide according to the present invention;

Pig. Figure 6 is a photomicrograph at a magnification of 110X showing the penetration of titanium into the treated specimen of Figure 5;

Pig. FIG. 7 shows an X-ray radiation scan with an electron probe microanalyzer (EPMA) of the Ti-K surface layer of the test specimen, the section of which in the Pig. 5 and 6 is shown;

Pig. 8 is a micrograph at 1100x magnification of that in Pig. 5, after heavy haul plating and polishing, to show the thickness of the deposit;

Pig. 9 to 16 EPMA line scans of each of digits 1 to 8, as in Pig. 5 indicated;

Pig. 17 shows an EPMA scan of the Ti-enriched, in Pig. marked zone;

Pig. Figure 18 is a composite micrograph taken with a right and left halftone scanning microscope (SM) of a steel matrix molybdenum fused to a solid molybdenum electrode by the method of the present invention; the left half is a 655x magnification and the right half is a 1965x magnification of the area marked in the left half;

Fig. 18A is a composite micrograph, with right and left halves, of another steel matrix fused to molybdenum from a solid molybdenum electrode using the method of the present invention; the left half is a 1310-fold magnification and the right half a 3930-fold magnification of the area marked in the left half;

Pig. 19 is a diagram of a SEM / ΕΡΜΑ 'in Pig. 18, which shows the fusion of molybdenum with the steel;

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Pig. FIG. 19A is a diagram of a scanning microscope scan of the type in Pig. 19, showing the fusion of molybdenum with the steel;

Pig. Fig. 20 is a SEM micrograph at 1310X magnification of a steel matrix with which tungsten was fused by a solid tungsten electrode by the method of the present invention;

Pig. 21 is a diagram of an SEM / EPMA scan of the type in Pig. 20, which shows the fusion of tungsten with the steel;

Pig. Fig. 22 shows a green and left half, a copper matrix, with which molybdenum was fused from a molybdenum solution using the method according to the invention. The left half is a 1250x magnification and the right half is an 8x magnification of the areas marked in the left half;

Pig. Fig. 23 is a diagram of an SEM / EPMA scan of the type in Pig. 22, which shows the fusion of molybdenum with copper;

Pig. Figure 24 shows a composite SEM micrograph, with right and left halves, of a steel matrix fused to molybdenum from a 1 / lolybdenum solution using the process of the invention. The left half is a 1250x magnification and the right half is an 8x magnification of the areas marked in the left half;

Pig. Fig. 25 is a diagram of an SEM / EPMA scan of the type in Pig. 24, which shows the fusion of molybdenum with steel;

Pig. 26 is a composite micrograph, with right and left halves, of a copper matrix to which tungsten has been fused from tungsten solution using the method of the present invention. The left half is a 1250x magnification and the right half is an 8x magnification of the area marked in the left half;

Pig. Figure 27 shows another SEM micrograph of the sample of Pig. 26

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in a 10 000 magnification of a part of the area marked in Fig. 26;

28 is a diagram of a SHI / ΕΡΜΑ scanning in Figures "2% and the sample shown 287OI.

Figure 29 is a composite micrograph, with right and left halves, of a steel matrix to which tungsten has been fused from a tungsten solution using the method of the present invention. The left half is a 1310x magnification and the right half is an 8x magnification of the area marked in the left half;

FIG. 30 is a diagram of an SEM / EPMA sampling of FIG. in Fig. 29, showing the fusion of tungsten with steel;

Fig. 31 is a composite microphotograph, with right and left halves, of a copper matrix to which indium has been fused from an indium solution by the method of the present invention. The left half is a 1250x magnification and the right half is an 8x magnification of the area marked in the left half;

Fig. 32 is a diagram of an electron microprobe scan of the sample shown in Fig. 31;

Fig. 33 is a composite SEM micrograph, with right and left halves, of a steel matrix to which indium has been fused from an indium solution using the method of the present invention. The left half is a 625x magnification and the right half is 8x the area marked in the left half;

Fig. 34 is a diagram of an SEM / EPMA scan of the sample shown in Fig. 33;

Fig. 35 shows a composite SSM micrograph, with right and left halves, of a copper matrix to which nickel was fused from a base solution using the method of the present invention. The left half is a 1250x magnification and the right half is an 8x magnification of the area marked in the left half;

Pig. Fig. 36 is a diagram of an SSLi / ΕΡΜΑ sample of the sample shown in Fig. 35;

FIG. 37 shows a composite microstructure with right and left half, a steel matrix, to which nickel has been fused to a nickel solution using the process of the present invention. The left half is a 1310x magnification and the right half is an 8x magnification of the area marked in the left half;

Fig. 38 is a diagram of an SEM / EPMA scan of the sample shown in Fig. 37;

Fig. 39 is a composite micrograph of a copper matrix 'fused with gold'. The left half is a 1310x magnification and the right half is an 8x magnification of the area marked in the left half;

Fig. 40 is a diagram of an SEM / EPMA scan of the sample shown in Fig. 39, showing fused gold with the copper matrix;

Figure 41 is a composite micrograph, with right and left halves, of a steel matrix to which gold has been fused using the method of the invention. The left half is 1310x magnification and the right half is 8x magnification in the left half marked area;

Fig. 42 is a diagram of a SEH / EPMA scan of the sample shown in Fig. 40, showing gold melted into the steel matrix;

FIG. 43 shows an SEM micrograph magnified 10,000 times by a copper matrix with which chromium has been fused from a first ghrome solution using the method according to the invention. FIG.

Fig. 44 is a diagram of an SM / EPMA scan of the sample shown in Fig. 43 showing the fusion of chromium with copper;

FIG. 45 shows an SEM micrograph magnified 10,000 times from a steel matrix with chromium using the

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method according to the invention was fused from the abovementioned first chromium solution;

Pig. Fig. 46 is a diagram of an SM / EPMA scan of the sample shown in Fig. 45, showing the fusion of chromium with steel;

Pig "47 a composite SEM micrograph, with right and left halves, a copper matrix with which chromium was fused using a second chromium solution using the process of the present invention." The left half is magnified 625 times, and the right half is 8 inches tall. magnify dea in the left half marked area;

Pig. Fig. 47A shows a more magnified SEM micrograph of the enlarged area of Fig. 47 at a magnification of 10,000X;

FIG. 48 is a diagram of an SM / EPMA sample of the type shown in FIG. 47, which shows the fusion of chromium with copper;

Figure 49 shows a composite SM microstructure with right and left half, a steel matrix, with which chromium was fused from a second chromium solution using the method of the invention. The left half is a 1250x magnification and the right half is an 8x magnification of the area marked in the left half;

FIG. 49A shows a more magnified SEM micrograph of the enlarged area a of FIG. 49 at a magnification of 10,000 times j. FIG

Fig. 50 is a diagram of an SMd / EPMA scan of the sample shown in Fig. 48, showing the fusion of chromium with steel;

51 shows a composite micrograph, with right and left half, of a copper matrix, with which cadmium was fused using a first cadmium solution using the method according to the invention; the left half is a 1310x magnification and the right half is a 5x magnification of the marked area;

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Pig. Fig. 52 is a diagram of an SEM / EPMA scan of the type in Pig. 51, which shows a fusion of cadmium with copper;

Fig. 53 is a photomicrograph 1150x magnification of a steel matrix fused to cadmium from a second cadmium solution using the method of the invention;

Pig. FIG. 54 is a diagram of an SEM / EPMA scan performed in Pig. 53, which shows the fusion of cadmium with steel;

Figure 55 is a composite micrograph, with right and left halves, of a copper matrix to which tin has been fused using the method of this invention to a first tin solution. the left half is a 655x magnification and the right half is an 8x magnification of the marked area;

Fig. 56 is an SEM / EPMA scan of the sample of Pig * 55 showing the fusion of tin with copper;

Pig. FIG. 57 shows a composite micrograph, with right and left halves, of a copper matrix to which tin has been fused from a second tin solution using the process according to the invention. the left half is a 326x magnification and the right half is an 8x magnification of the marked area;

FIG. 58 is an SEM / EPMA scan of the sample of Pig. FIG. 57, which shows the fusion of tin with copper;

Pig. Figure 59 shows a composite SEM micrograph, with right and left half, of a steel matrix to which tin has been fused from the second tin solution using the method of the present invention; the right half is a 1310x magnification and the left half is an 8x magnification of the marked area;

Pig. 60 is a SEM / EPMA scan of the type in Pig. 59, which shows the fusion of tin with steel;

Pig. Fig. 61 shows an SEM micro pickup in a 5200X magnification

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a copper matrix with which cobalt was fused using a process according to the invention to a first cobalt solution;

Pig. FIG. 62 is a SEM / ΕΡΜΑ scan of the sample shown in FIG. 61, showing the fusion of cobalt with copper;

FIGS. 63 and 63A are micrographs of a copper matrix fused to silver with a first silver solution using the method of the present invention;

Pig. FIG. 63 shows a composite wherein the left half is 625 times magnification and the right half is 8 times magnification of the marked area; FIG.

Fig. 63A shows a more magnified SEM micrograph of the enlarged portion of Fig. 63 at 10,000X magnification;

Fig. 64 is an SEM / EPMA scan of the sample of Fig. 63 showing the fusion of silver with copper;

Fig. 65 shows an SEM micrograph magnified 10,000X from a copper matrix to which silver has been fused from a second silver solution using the method of the present invention;

FIG. 66 shows an electron microprobe scan of the sample of FIG.

65, which shows the fusion of silver with copper;

In the diagrams representing figures, from FIG. 19 to FIG.

66, the vertical axis is logarithmic, while the horizontal axis is linear. And in these graphs, the surface layer was determined at the point where the concentration (ingot) of the matrix and the element fused thereto are both 50 % , as evidenced by the extensions.

1 and 2 of the drawings show in a general perspective view of the plant according to the invention, which is used to carry out the method according to the invention »

In Fig. 1, which illustrates a solid-by-solid process, the Hummer 10 designates an energy source and 11 an oscillator »

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One side of the oscillator assembly is connected to the electrode 13 by a fitting 12. The fitting 12 is provided with a rotatable chuck and has an enable switch which controls the rotational speed of the electrode 13. The speed is variable between 5000 and 10,000 revs / min.

The electrode 13 consists of the material to be fused with the matrix. The matrix or substrate for which the method is to be applied and treated is indicated at 14. The matrix is also connected to the other side of the ocillary output by a terminal 15 and line 16.

These connections make the electrode positive and the matrix negatively charged when the signal is applied.

In Pig. 2, the corresponding components are numbered accordingly. However, in this embodiment, the process used may be characterized as a "liquid-on-the-grounds" process. In this plant, the material to be fused has e Porm and is contained in a container 17. The vessel 17 is through a tube 18 with an electrode 19 connected. Electrode 19 is a plate provided with an insulated handle 20 to which one side of the output of oscillator 11 is connected. This output is fed into a main channel 21 in-electrode 19. Channel 21 is provided with a series of side channels 22 which are open to the bottom of the electrode 20. Flow from the container 17 is by gravity or "by means of a pump and can be regulated by a valve on the handle 20 as in Figure 23. For further control, more uniform distribution of the solution and prevention of inclusion of premixtures is the surface of the electrode 19 preferably coated with a permeable membrane such as cotton or hylon.

It has been found that in order to achieve the merger

2, the application of 50 000 watts / cm or alternatively the application of a current of the order of 10 000 A / cm is required.

For practical reasons, 10 000 A / cm can not be constant

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without damaging the matrix to be treated ·

However, Ea has proved to be feasible in applying a pulse signal of 2.5 micro-seconds to the electrode for up to 28.6 nanoseconds with a strength of 3 A, whereby

2 melt on an area of approximately 0.3 mm.

In order to perform a fusion on a surface with the system shown in FIG. 1, the electrode 13, matrix 14 and the oscillator assembly are connected together as shown.

The worker guides the rotating electrode 13, which is in contact with the surface of the matrix, at a certain speed across the matrix surface to apply and fuse the electrode material to the matrix.

It has also been found that the continuous application of an alternating signal generates considerable heat in the substrate or matrix, and to eliminate this accumulation of heat and avoid welding, the signal generated in the system according to the invention is a half-wave signal representing the dissipation of heat allows ·

As known to those skilled in the art, any material, both matrix and material to be applied, will have resistivity values. Thus was the circuit to be associated with any change in one of these _'substances or both a change in the specific resistance \.

In Fig. 3 , R ₁ = the resistance of the electrode

R ₂ = the resistance of the matrix and

R, = the resistance of the circuit of 10 and 11.

A change in R ₁ and R ₂ will result in changes in the frequency of the signal generated and in the amplitude of that signal.

As already mentioned, a signal with an amplitude of 3 A is assumed to have the preferred amplitude. When the amplitude is higher, decarburization or burning of the matrix occurs, and at an underlying amplitude, hydroxides are formed in the interface.

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Fig. 4 is an achematische diagram of an oscillator circuit, viie it is applied in a erfindungagemäßen plant »

In this circuit, a power source 30 is connected to the input and a capacitor 31 is connected to the input iat. One side of the capacitor 31 is connected to the LC circuit 32 which includes a control roll 33 and a condenser 34 connected in parallel ,

The LC circuit 32 is connected to one side of a Kriatalloszillatorschaltung, the crystal 35 »inductor 36» HPN-Transiator 37 and the RC circuit with the Regelvjiderstand 38 and.the capacitive. Resistance 39 includes «

This Oazillatorstromkreia is, t connected to the output 50, on one side by the capacitor 40 and on the other side by diode 41, at the output 50 a Halbvjellenaignal. to create"

In the plant actually used, the individual constituents had the following characteristics j

31 = 1.2, u-Farad

32 = 0.3 "picofair

33 * 0 - 25 Millihenry

35 = 400 - 30 kHz

36 = 20 millihenries

37 = HPH

38 = 3.5 / u Farad 39 = 0 - 500 0hm

 40- = 400 / U Farad 41 = diode

To keep the amplitude of the signal at 3 A, R .. resistor 38 is varied; For varying the frequency, the choke coil 33 varies.

If G = the capacitance of the circuit of Fig. 3 and R ^, R ₂ and R ^ are the resistors characterized above, then it can be assumed that the optimum frequency of the fuse signal F _Q can be determined from the following formula

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ρ - J - - Formula I

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wherein: L = R-, Rg-Ro

and G = capacitance of the circuit.

L and G can be determined by any well-known method,

F depends on the material to be treated and the material to be applied, but will be in the range of 400 Hz bia 35 MHz. · It is assumed that the frequency determines the speed of the process.

The same is measured to merge a certain area.

ο As approximately 0.3 mm are melted by each discharge, the feed rate is determined by the following formula *

F ₁ χ 0.3 σ 60 mm / minute

Feed rate = formula II

 and

ρ A = area to be coated in mm.

F = the number of discharges per second

As explained above, the resistances R .. and R ₂ can be measured by ) any known method.

However, it has been discovered that the measurement of the resistance in the liquid phase may not be consistent. In this case, the resistance is measured by a standard method. Two electrodes at a distance of 1 cm and

with an area of 1 cm are placed in a bath of the liquid phase and the resistance is measured after a delay of 20 seconds. Once the variable parameters have been determined and the equipment, matrix and probe have been connected as shown in Figs. 1 and 3, the probe 13 is passed over the surface of the matrix at the fixed speed, contacting the same.

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The speed is also considered to affect the quality of a fusion, whereby at a speed of 5000 rpm a surface finish is obtained in a non-uniform 200 to 300 rpm, and at a speed of 10 000 rpm. the surface finish is essentially a 15./tun version "Pig. 2 is in the same way as Pig's. 1, and the method is substantially the same, except that a liquid having a fixed electrode is used.

From the following specific examples, the process will become even clearer.

In each of these examples, the electrode was connected as will be apparent from the description so that after charging, the electrode is positive and the matrix is negatively charged.

The solid-by-solid process is illustrated by Examples I, II, IIA, III and IV »

Example I

Tool steel Atlas A151 01 was connected as matrix 14 to the plant of Fig. 1 and as electrode 13 was used as Kennametal KI65 designated titanium carbide *

The following are the characteristics and treatment conditions:

Matrizwiderstand 0.002 0hm

Probe resistance 0.026 ohms

Circuit resistance - 0.01 ohms

Frequency (F ₁ ) 12 kHz at 4.62 / U Farad

Voltage 3 volts

Application speed 50 cm / minute

Handling depth »40 / um

Surface thickness increase ~ 0.5 / um

The results from the treatment of the tool steel Atlas AI5I 01 with the titanium carbide are shown in the micrographs and the spectrometer scans of FIGS. 5 to 17.

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The polished and titanium carbide-treated steel was examined by SEM / ΕΡΜΑ and showed the appearance of Fig. 5. X-ray photographs were taken of each of the numbered locations indicated in Pig, 1, and these are shown in the graphs of Figs and they correspond to positions 1 to 8 respectively ·

FIGS. 9, 10 and 11 show spectra of the base metal.

Figs. 12 to 16 show the presence of a small titanium tip whose. Height at crossing. the zone did not change noticeably ·

As is apparent from Fig. 6, the approximate width of the zone in which titanium was detected is about 50 μm, although this dimension changed with the length of the probe.

Examination of the surface layer using a Hikro probe analyzer gave the Ti-KoC X-ray image shown in Figure 7, which shows that the amount of titanium was fairly constant to a measured depth of about 40 / um.

The sample was then covered with a thick nickel coating and polished again. As can be seen from Fig. 5, the prepared scanning micrograph shows a surface layer of about V 2 microns. 17 is an X-ray spectrum of this layer.

A hardness test of the coated steel sample was then carried out and the results listed in Table I were determined *

Table I

Knoop hardness tests burden 100 gram (2) Distance to the edge of the specimen K H Ii 516 (Inch) (D 728 0.0005; _Ti enriched zone 578 770 0.001) 650 872 0.0015 536 1006 0,002 655 1006 0.0025 790 0,003 863

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(Porting of Table I) 955 453 0,004 536 - 0.005 243 148 0.01

How one. will determine, the hardness characteristics of the steel have been significantly improved ·

Example II

Steel 1018 was made with the plant of Pig. 1 is connected as the matrix 14 and the electrode 13 used molybdenum, Mo type 1. The steel was ϊ / 2 inches wide, χ ^1/4 inches thick χ V / 2 inches long, the molybdenum 1 inch long with a diameter of 4 mm · The applied frequency was 43.31 kHz and the rate of electrode rotation was approximately 12,000 rpm.

The surface of the steel was abraded to a surface finish of 600 grit. The tip of the electrode was passed by hand over the surface of the steel sample in straight juxtaposed lines. The process was repeated in to cover the whole surface. Under the light microscope, small beads of molten and resolidified material could be detected at 40X magnification.

Like from Pig. 18 can be seen, the fusion of molybdenum with the steel is clearly visible.

The results of electron microprobe scanning of the interface showed that molybdenum is present to a depth of at least 15 μm, as shown in the table below and FIG.

evident. Mass Mo Massel Pe Depth, / um 6.9 93.1 1 7.6 92.4 2 7.0 93.0 3 7.5 92.5 4 6.6 93.4 10 6.0 94.0 15

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Microhardness readings were made on the sample cross section and gave the following results:

Knoop hardness number " load depth from the surface 493 200 g- 30 yum

198 200 g 40 / um

The average KBU of the untreated steel was 188, the hardness of the same steel after heater serabschreckung was 285 (KHII) at 200 g,

The hardness of the same steel after heating to 900 ⁰ G and Waas

Beiapiel HA ·

The same matrix and electrode as well as the same procedure as in Example II were applied at a frequency of 30.63 kHz and the same speed.

Small beads of molten and resolidified material were detected under the light micro-top.

Like from Pig. 18A, the fusion of molybdenum with steel was quite clear.

The results of electron microprobe scanning of the interface revealed that molybdenum was present to a depth of at least 50%, as shown in the table below and in FIG

Pig. 1-9A shown becomes: Mass Mo Mass / $ pe depth * /around 8.8 91.2 10 11.2 88.8 20 3.6 96.4 30 3.6 96.4 40 2.5 97.5 50

Knoop microhardness measurements were made on the cross section of the sample. The following results were obtainedί

Depth, / um KHE - burden

15,375,200

25,506,200

40,445,200

150 227 200.

500 - 188 200

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The hardness values in Examples II and HA above Kf5 28 result from the presence of molybdenum.

Example III .

Steel having the same specifications as in Examples II and HA was connected as a matrix 14 to the plant of Fig. 1, and tungsten carbide (Kennametal grade Hr, 68) served as the electrode 13. This electrode had a diameter of 5 ram and was 1 inch long »

The applied frequency was 26.20 kHz and the speed of the lead electrode rotation was approximately 12,000 rpm.

As a procedure, the same as in Examples II and HA was used.

As shown in Fig. 20, tungsten was fused with the steel matrix. The results of electron microscopic analysis of the sample show that tungsten is present to a depth of at least 80 μm, as can be seen from Fig. 21 and the table below

Depth, / um Mass% TW Massel Fe 1 24.4 75.6 5 27.5 72.5 10 1.7 • 98.3 20 1.8 98.2 50 1.1 98.9 80 1.7 98.3

Knoop microhardness measurements were made on the sample cross-section. The following results were determined:

Depth, to KHN load

28 908 200 g

45 '718 200 g

75 329 200 g

120 220 200 g

The hardness of the untreated sample is approximately 188 KHTT and after heating to 900 ⁰ G and quenching at 285 KHI.

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It is clear from the above that by treating the steel matrix: the surface hardness is improved and that is for those. Use cases where surface hardness plays an important role are very useful *

For melting a second conductive chemical EIementes in the solid matrix of a first conductive chemical element using a solution of the second conductive chemical as well as for ^ ny solution, the method at ambient temperature, 20 ⁰ G was carried out in the following manner.

The metal die 14 was connected to the circuit as described above. The frequency was determined according to the formula given above, and the solution contained in the container 17 was applied by passing the electrode over a surface of the first metal for different lengths of time, as determined by formula II. In order to ensure a uniform distribution of the solution of the second metal on the surface of the first metal, the electrode was covered with cotton gauze or nylon. It is clear that other substances can be used. This measure also served to limit the contamination of the solution when using graphite electrodes. In these, there is a possibility that graphite particles in the course of the movement replace »

The treated samples were then scalped to obtain a cut sample, washed in cold water, sonicated, embedded in plastic and ground and polished to obtain a flat surface and a smooth edge. For other samples of softer metals that were likely to break off the edge during sanding, two sections were bonded to the treated surfaces, as previously embedded and ground and polished.

After embedding, the sample was etched using ammonium hydrogen peroxide for steel, the ferrous substrate, Nital, and for copper, the ferrous substrate.

In the course of some application work it has been found that sometimes settings of either frequency or up *

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were required. These tiars have become necessary as a result of changes in the solubilizing composition or deviations in the matrix.

Semiquantitative bulk electron probe analysis of the enameled interfaces was performed using Energy Diaperaive X-Ray Spectroscopy (EDX) and Scanning Microscope (SEM).

The surface of the embedment plate was made conductive by depositing an approximately 20 μm thick carbon layer on it in a vacuum evaporator. This measure was used to prevent the build-up of electrical charges on an otherwise non-conductive material and the resulting instability of the SEM device. Image taken · Carbon which does not produce EDX detectable radiation was preferred over a more conventional metal coating to prevent interference of such a coating in elemental analysis »

The operating conditions of the SM were chosen to minimize spurious signals and continuum radiation while providing the best possible spatial resolution.

The general conditions used for elemental analysis by EDX were as follows: j

Acceleration potential endopening

Spot size beam current

Working Distance Magnification Factor Specimen Angle Derivative Angle Count Rate

Time under tension

The energy calibration was tested using Al-Kd emission at 1.486 keV and Cu-K at 8.040 keV.

10 - 20 kV - 300pA 200 - 300 34 mm 50 nm - 10 000 100 to the beam 12 - 5000 - 2000 Hz perpendicular 180 a 225 ° 800 60 -

23671 1

A standard half-quantitative analysis was used to determine the elemental concentration using certified cover fabrics (ITBS 478, 78 % Cu - 27 % Zn and WBS 479a, Hi, 11 %, Gr 18 $, Pe) to confirm the results. Multiple analyzes of reference materials were in excellent agreement with the confirmed values of NBS. An average accuracy of + 1 % was achieved. A size of analyzed volume was calculated from the following equation 1 $. ,

pR _(x) = 0.064 (E _O 1 ⁶⁸ - E _C 1 ⁶⁸ )

in which mean

R / ν the mass range (the X-ray generation volume) ρ = density of the material analyzed

E _Q = the acceleration potential

E_ = a critical excitation energy

The diameter of volume analyzed was calculated for typical analyzed elements and found to be ί 0.46

Gu 0.39

Pe 0.55

W 0.30

In order to determine the diffusion depth, a static beam was conducted across the interface at intervals larger than the above-mentioned mass range. This ensured the accuracy of the analysis *

The results of the element concentration were given for each point measured in the mass at the fusion interface.

In the various examples that will be described, the second conductive chemical element, i. the element to be diffused into the matrix exists. In some solutions

ι / ie

are also small amounts of MetallipnenVvorhanden · It is believed that these metal ions "must be present as a complexing agent ^v, to facilitate the merger takes. Small amounts of organic catalysts such as acacia, hydroquinone,

t- sJ KJ / II VJ>

Bone glue, pepsin, dextrin, licorice or their equivalents may also be present.

Wetting agents such as sodium lauryl sulfate or its equivalent are normally used.

If necessary, pH-modifying agents such as ammonium hydroxide or sulfuric acid are usually added to achieve the required pH.

Some other solutions require complexing agents for the second chemical conductive element that preclude precipitation of the second element. Such agents are, for example, citric acid or sodium pyrophosphate or ethyldiaminetetraacetic acid or its equivalents.

In some solutions, a suitable buffer is also provided, if required.

The water is always demineralized.

And for certain applications in which the appearance of the product must be appealing, small amounts of brightening agents such as formaldehyde, carbon disulfide, benzenesulfonic acid or their equivalents can be used ·

In these examples, unless otherwise specified, ASA 1018 steel matrix and ASOM B-1333 copper alloy 110 are used.

Example IV

Steel Atlas A151 1020 was attached as matrix 14 to the plant of Fig. 2, and a 10% solution of ammonium molybdate in water was placed in vessel 17.

The following characteristics and treatment conditions were used

Matrix resistance 0.0018 ohms

⁺ Probe resistance 150 kilohms

Circuit resistance 0.01 ohms

Frequency 650 Hz at 0.4 picofarads

Contact area 2 cm ²

23 6 7 11 ü

Speed 60 cm / minute

Treatment depth «0.5 / um

Surface elevation "& 15 / um

Determined by measuring 1 cm of panels 1 cm apart after a 20 second delay.

The sample of Example IY was subjected to a cotton corrosive teat. 25% sulfuric acid was allowed to act on the surface for 20 minutes at 325 ^° C without any surface penetration.

) Example Y

An aqueous solution with the following composition was prepared!

Harness grams / liter

Sodium molybdate 37.8

Iron (II) ammonium sulfate 7

Iron CIII) ammonium sulfate 8,6

Citric acid 66.0

Water (distilled) 997 ml

Katriumlaurylsulfat 0.5 ammonium hydroxide. until the required pH

Acacia gum (gum arabic) 0.1 - 0.2

/) Formaldehyde 7.5 ml

The solution showed the following characteristics:

pH = 7.5

resistivity = 19 ohm-cm

Mo ⁺ concentration = 1.8 mass

= 0.10 mass. = 0.10 mass

The concentration of Mo ⁺ can be varied from 1.5 to 2.5 masses; the pH may be from 7.2 to 8.2 and the resistivity may be between 17 and 25 ohm-cm.

Re ectuations

Matrix i copper

Electrode: graphite

1 1 U

Electrode coating: Baumwöligerebe

Frequency: 9.09 kHz

Application speed: 736.2 mm / minute

Date of application ί 2 minutes

It is believed that in the illustrated in Examples 7 and VI solutions, the presence of iron (II) - ions is used and iron (III) to reduce aen valence state of Mo to a lower valence state.

Although the iron appears to be transferred simultaneously, as shown in Fig. 23, the iron obviously has no material influence on the characteristics of the matrix or molybdenum.

An examination of the sample with a light microscope shows a continuous molybdenum coating, which is free from pitting and has a dark silver color.

As in the table below and Pig. 23, it is apparent from an SM / EPMA scan of the interface between the matrix and the deposited metal that molybdenum has been fused to a depth of at least 4 μm at a surface deposition of approximately 1 μm.

table

Concentration (mass)

Depth, /around element Konz 0.5 Mo Fe Gu 65.4 19.9 14.5 1.0 Mo Fe Gu 58.4 10.9 30.5 2.0 Mo "Pe Gu 6.6 0.8 92.5 3.0 Mo Fe Cu 2.9 0.4 96.6 4.0 Mo Fe Cu 0.9 0.0 98.9

ZJbV 1} O

Beiapiel 71

Ba was prepared an aqueous solution having the same composition as in Beiapiel® V and applied under the following conditions:

Reaktionabedingungen

matrix

electrode

Electrode coating Fre quenz

Application speed Application duration

= Steel (ASA 1018) = graphite = cotton fabric = 4.11 kHz = 739.8 mm / minute = 3 minutes

Examination under the light microscope revealed a continuous dark-purple colored surface.

The micrograph of Fig. 24 shows the deposition of a substantially uniform layer of molybdenum in a thickness of 1 μm and with uniform density.

As can be seen in Figure 25, an SEM / ΕΡΜΑ scan of the interface between the substrate and the deposited metal shows that molybdenum was present to a depth of at least 10 microns, with an alpha-olefin gradient as shown in the table below ·

• Table

Depth, / um

element

Concentration (mass)

81.0 19.0

2.2 97.8

0.8 99.2

0.6 99.4

Ea, an aqueous solution of the following composition was prepared

0.5 Mo Fe 2 Mo Fe 3 Mo Fe 10 Mo Fe Beiapiel VII

IT ame grams / liter

Sodium Vsolframate 31,40

EiaendlD-ammonium sulfate at 8.63

Iron (II) sulfate 4.98

Citric acid 66,00

Water (distilled) 1000 ml

Ammonium hydroxide "to the required pH-value

Sodium lauryl sulfate 0.1

Formaldehyde 5 ml

The solution had the following characteristics; pH = 7.99

resistivity = 22 ohm-cm W * ⁶ = 1.75 mass

Pe ⁺² = 0,1 mass

Pe ⁺ - ³ = 0,1 mass

The ViZ ⁺ concentration can vary between 1.6 and 2.5 mass; the pH may be from 7.5 to 8.5 and the resistivity may be between 18 ohm-cm and 24 ohm-cm.

Reaction terms

Matrix = copper

Electrode = graphite

Electrode coating = tree violet gauze

Frequency = 3.83 kHz

Application rate = 689.4 mm / minute

Application time = 3 minutes

As from the micrographs of Pig. 26 and 27, the sample showed a uniform tungsten layer with a thickness of approximately 1 micrometer. An SEM / EPMA scan showed a merger of wolf space to copper to a depth of at least 5.0 microns as compared to the table below and FIG. 28.

Table depth, / um

1.0 2.0 3.0 4.0 5.0

Concentration (mass Pe %) W 38.5 Cu 37.3 2.1 24.2 4.8 0.3 93.1 0.5 0.2 99.2 0.7 0.2 99.1 0.3 99.5

1 year %

Example VIII

Ea was prepared an aqueous solution having the following composition

IT ame ^v Grams / liter

Hatrium tungstate 34.00

Iron (II) sulfate ¹ 4.98

Iron (II) ammonium sulphate 7.02

Ferric ammonium sulfate 8,62

Citric acid 66,00

Water (distilled) 980

Ammonium hydroxide "to the required pH

Sodium lauryl sulfate 0.10-

Notej It is possible to use either 1 or 2 ·

The solution had the following characteristics:

pH = 8

resistivity = 20.9 ohm-cm

W ⁺⁶ = 1.9 mass

Pe ⁺² = 0,1 mass

Pe ' ¹ ' - '= 0,1 mass

The concentration of tungsten can vary between 1.6 and 2.5 masses; the pH can be from 7.5 to 8.5 and the. resistivity may be between 18.8 ohm-cm and 22.8 ohm-cm.

reaction conditions

Matrix = steel (ASA 1018)

Electrode = graphite

Blektrodenüberzug = cotton gauze

Frequency = 4.78

Application speed = 860.4 mm / minute

Application time = 3 minutes

Examination of the sample with the aid of SEM / ΕΡΜΑ, Fig. 29, showed a tungsten layer of approximately 0.5 / do, and as is clear from Fig. 30 and the table below, tungsten could be up to a depth of at least 3 / ura.

u / ι ι u

table element Concentration (mass) Depth, / do W W W W 52 6 1 1.1 0.5 1 2 3 Example IX

An aqueous solution having the following composition was prepared

Harness grams / liter

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

The solution had the following characteristics: pH = 1.60

resistivity = 51.8 ohm-cm concentration In ⁺ = 1.75 mass

Concentration Al ⁺ - ³ = 0.077 mass

The indium concentration can vary between 0.2 and 2.2 masses; the pH may be from 1.60 to 1.68 and the resistivity may be between 48.8 ohm-cm and 54.8 ohm-cm.

reaction conditions

Matrix = copper

Electrode = graphite

Electrode cover = cotton gauze

Frequency = 4.75

Application speed = 855 now / minute

Application duration = 3 minutes

An examination of the sample under the light microscope and the scanning microscope showed a continuous surface that was free from structural defects, such as Pig. 31 shows «

As shown in the table below and Pig. 32, an SEH / EPHA scan of the interface between the copper matrix and the indium layer revealed a plot of approximately 1 / um and a fusion of indium to a depth of at least 4 / um.

table

Depth, / um element Concentration of indium (ingot) 1 In 90.3 2 In 5.5 3 In 4.3 4 In 3.6 Example X

The solution of Example IX was used and applied to a steel matrix i

reaction conditions

Matrix = steel (ASA 1010)

Electrode = platinum

Electrode coating = Hylongeviebe

! frequency = 6.29 kHz

Application speed = 1132.2 mm / minute

Application time = 3 minutes

As can be seen from Figs. 33 and 34, a smooth continuous layer of indium was deposited on the surface of the matrix to a thickness of approximately 1 μm. An SEM / EPMA scan, Figure 34, of the interface and the table below shows a fusion to a depth of at least

Fe (Massed)

8.6 94.8 99.0 99.1

table Depth, / um In (Massel) 0.5 91.4 1.0 5.2 2.0 1.0 3.0 0.9

236711 O

Pig. Figure 35 shows a solid nickel layer with uniform density and a thickness of approximately 1.5 / μm. Like the table below and Pig. As shown in Figure 36, an SM / EPMA scan of the interface between the matrix and the nickel layer showed that the yellow bia fused to a depth of at least 4 μm

has been. element pig Depth,, um Ni 92.6 / 1 Hi 4.5 2 Ni 3.3 3 Hi 1.0 4

Example XI

An aqueous solution of the following composition was prepared

Harness grams / liter

HickeKlD sulphate 248.9

HickeKlD chloride 37.3

Boric acid 24.9

Formaldehyde 3 ml / liter

Benzolaurofonic acid 10 ml / liter

Sodium lauryl sulfate 0.1

Water (distilled) 900

The solution had the following characteristics:

pH = 3.10

resistivity = 22.5 ohm-cm

Concentration of Ni = 6 mass%

The nickel concentration can vary between 2 and 10 % ; the pH may be from 3.10 to 3.50 and the resistivity may be between 17 ohm-cm and 26 ohm-cm.

reaction conditions

Matrix = copper

Electrode = graphite

Electrode cover = cotton gauze

Frequency = 7.50 kHz

• - 33 - I ό b 7 1 1 U

Application speed = 1350 mm / minute application time = 3 minutes

Example XII

Ea, the same solution was prepared as for Example XI and applied to a steel matrix;

Reaction conditions

Matrix = steel (ASA 1018)

Electrode = graphite

Electrode cover = cotton gauze

Frequency = 7.50 kHz

Application speed = 1350 mm / minute

Application time = 3 minutes

As in Pig. 37, the nickel layer is continuous and exhibits a substantially uniform thickness of about 1.5 / um.

As shown in Fig. 38 and the following table, hickel was fused to a depth of at least 3 μm.

Depth, / um element Concentration (mass) 1 Hi 95.9 2 ii 28.0 3 ii 0.7 Example Uli

An aqueous solution with the following composition was prepared:

I ame Grams / liter Goldchlorwasaeratoffsäure 2.5 Potassium ferrocyanide 15.0 potassium carbonate 15.0 Water (distilled) 1000 ml

This solution had the following characteristics; pH = 10.99

resistivity = 40 ohm-cm concentration of Au ⁺ ion = 0.14 mass

- 34 - JU / I I U

The pH can be varied between 3.70 and 11; the concentration of Au ⁺ ions may be from 0.1 to 0.5 mass% and the resistivity may be between 40 ohm-cm and 72 ohm-cm »

reaction conditions

Matrix = copper

Electrode = platinum

Electrode coating = tree violet gauze

Frequency; = 4.33 kHz

Application speed = 779.4 mm / minute

Application time = 2 minutes

Examination with the aid of the light and scanning microscope revealed a surface layer of gold with a thickness of approximately 1.5 μm. The layer was continuous and uniformly dense, as was Pig. 39 showed

A SUM / EPMA scan of the interface showed a fusion of gold to a depth of at least 3 / um as shown in the table below and Pig. 40 can be seen «

Depth «/ To Element Concentration (Massel)

0.5 Au 61.3

1.0 Au 9.6

2.0 Au 0.9

3.0 Au 0.5

Example XIY

An aqueous solution having the same composition as that of Example XIII was prepared.

reaction conditions

Matrix. = Steel

Electrode = graphite

Electrode coating = tree violet gauze

Frequency = 3.95 kHz

Application speed = 711.0 mm / minute

Application time = 2.0 minutes

Light and scanning microscope studies revealed a gold layer on the surface of approximate thickness

- 35 - L · O Ό ί \

1.0 / um. The layer was uniformly thick and dense, as Pig »41 shows»

An SEM / EPMA scan of the interface showed a fusion of Gold Idls to a depth of at least 4 * 0 / μm, as shown in the table below, and Figure 42.

Depth, / around element concentration (Massel)

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 XV

An aqueous solution of the following composition was prepared

Harness grams / liter

Chromium trioxide 150

Chromium sulfate 0.06

Sulfuric acid 2.15

Sodium hydroxyfluorosilicate 0.2

Carbon disulphide, 2 - 3 ml

Sodium lauryl sulfate 0.05

Water (distilled) to 1000 ml

This solution had the following characteristic pH = 0.6

resistivity = 12 ohm-cm concentration of Cr ⁺ = 7.8 mass

The pH can be varied between 0.6 and 1.0; the concentration of Cr ions can be between 3 and 20 mass and the resistivity can be between 11 ohm-cm and 14 ohm-cm,

Re ecting editions

Matrix = copper

Electrode = graphite

Electrode cover = cotton gauze

Frequency = 6.25 kHz

- 36 - £ O O / I I U

Application speed = 1125 mm / minute application time = 5.0 minutes

Studies with the light and scanning microscope have shown a chromium layer on the surface of approximately 1 / um thickness. The surface of the layer was irregular, but the layer appeared to be free from defects and was continuous, vii.θ pig. 43 shows ·

An SMi / IPMA scan of the interface revealed that chromium bia had fused to a depth of at least 3.0 / um, as shown

the table below element and FIG. 44 shows Depth, / um Cr Concentration (mass%) 0.5 Cr 94.0 1.0 Cr 32.0 2.0 Cr 1.8 3.0 1.0 Example XVI

An aqueous solution of the same composition as used in Example XV was prepared;

Re act ion d indents

Matrix = steel (ASA 1018)

Electrode = graphite

Electrode cover = cotton gauze

Frequency = 6.48 kHz

Application rate = 1166.4 mm / minute

Application time = 5.0 minutes

Examination with the light and scanning microscope revealed a chromium layer on the surface with a thickness of approximately 3.0 μm. It corresponded to that shown in FIG.

An SEM / EPMA scan of the interface showed a fusion of chromium to a depth of at least 5.0 / μm, as shown in the table below and Figure 46.

element Dimensions% Gr 100 Cr 97.2 Gr 20.8 Cr 2.8 Cr 2.1

Depth, / do

Beiapiel XVII

Ea was prepared an aqueous solution having the following composition:

Harness grams / liter

Chromium (III) chloride sodium chloride ammonium chloride boric acid

Dimethylformamide 400 ml

Sodium acetate 3.0

Hatrium latiryl sulfate 0.5

Water (distilled) to 1000 ml

This solution showed the following characteristics: pH = 3.0

resistivity = 17.4 ohm-cm concentration of Gr = 2.5 to 3.5

The pH can be varied between 2.5 and 3 »5; the concentration of Cr ⁺ ions may be between 1.8 and 5 mass and the specific value may be 16 ohm-cm to 0hm-cm.

reaction conditions

Matrix = copper

Electrode = graphite

Electrode cover = cotton gauze

Frequency = 6.85 kHz

Application speed = 1251 mm / minute

Application time = 3.0 minutes

Examination with the light and scanning microscope revealed a chromium layer on the surface of approximately 0.5 / μm thickness.

ό ö / i IU

The layer was feat and continuous, as shown in Figs. 47 and 47A.

An SEM / ΕΡΜΑ scan of the interface resulted in a fusing of chromium to a depth of at least 3.0 / μm, as shown in the table below and Fig. 48.

Depth, / around element concentration (Massel)

1 Cr - 21.2

2 Cr 4.0

3 Cr 0.9

Example XVIII

An aqueous solution having the same composition as prepared for Example XVII was used

reaction conditions

Matrix = steel (ASA 1018)

Electrode = graphite

Electrode cover = cotton gauze

Frequency = 6.85 kHz

Application speed = 1251 mm / minute

Application time = 3.0 minutes

Examination with the light and scanning microscope revealed a chromium layer on the surface with a thickness of approximately 1.0 / μm. The surface of the layer appeared to be somewhat irregular, but the layer was firm and free from defects, as shown in FIG. 49 and 49A show «,

An SEM / EPHA scan of the interface showed a fusion of chromium to a depth of at least 3.0 / μm, as shown in the table below and FIG. 50.

Depth, / around element concentration (Massel )

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

\ j / ι \

example

Ea, an aqueous solution of the following composition was prepared

Harness grams / liter

Gadmium chloride 6,74

Sodium diphosphate 54

Water (distilled) 1000 ml

Liese solution had the following characteristics pH = 10

resistivity = 33 ohm-cm concentration of Cd = 0.32 mass

The pH can be varied between 10 and 10.2; the concentration of Cd ions may be between 0.2 and 0.5 mass and the resistivity may be 28 ohm-cm to 35 ohm-cm.

reaction conditions

Matrix = copper

Electrode = graphite

Electrode coating = cotton gauze

Frequency '= (1) 7.29 kHz; (2) 7.91 kHz

Application speed = (1) 1312.2 mm / minute;

(2) 1423.8 mm / minute

Application time = (1) 1.0 min; (2) 3.0 min.

In this example, the solution used was initially as described above, applied according to the conditions indicated as (1). A second solution, cited in Example XK, was then applied under the conditions indicated as (2).

Examination with the light and scanning microscope revealed a cadmium layer on the surface with a thickness of approximately 4 μm. This layer was, like Pig. 51, not homogeneous, but an SEM / EPMA scan of the interface showed a fusing of cadmium to a depth of at least 9 / μm, as shown in the table below and Pig. 52 show.

L. yy U /

"W

Depth, / um element Concentration (mass) 2 CD 77.4 3 CD 65.2 4 CD 6.7 VJL CD 1.2 6 CD 0.48 7 CD 2.1 8th CD 2.9 9 CD 0.89 Example XX It was an aqueous solution following composition manufactured: urine Grams / liter cadmium sulfate 26.65 sodium chloride 8.7 boric acid 15.0 Al um ini umsulf at 17.5 0.25 5.0 2.5 0.5 1000 ml Acacia gum (gum arabic) Sodium tetraborate benzenesulfonic Sodium lauryl sulfate Water (distilled)

This solution had the following characteristics: pH = 3.40

specific resistance = 54.0hm-cm concentration of Cd

+2

= 1.1 %

The pH can be varied between 3.2 and 3.5; the con-

+2 concentration of Cd ions can be from 1 to 4 masses and the resistivity can be between 45 ohm-cm and 55 ohm-cm.

Reaction terms

matrix

electrode

Electrode coating Pre quenz

= Steel = platinum = nylon cloth = 13.7 kHz

L JQ / I \ U

Application speed = 2466 mm / minute application time = 2 minutes

Examination with the light and scanning microscope revealed a cadmium layer on the surface with a thickness of approximately 1 / um. The surface of the layer was irregular, but it was firm and continuous, as from Pig. 53 can be seen.

An SEM / EPMA scan of the interface showed a fusing of cadmium to a depth of at least 4 / um as shown in the table below and Pig. 54 can be seen.

Depth, / around element concentration (Maaae ^)

73.3 8.8 1.4 1.2 1.1

An aqueous solution with the following composition was prepared:

IT ame grams / liter

Tin dichloride 77.3

Sodium hydroxide 66.0

Sodium acetate 14,7

Water (distilled) 1000 ml

This solution had the following characteristics j pH = 12.4

resistivity = 8.6 ohm-cm

+2

Concentration of Sn ions = 4 mass%

The pH can be varied between 11.2 and 12.7; the

+ 2

Concentration of the Sn ions may be between 2 and 5 mass and the resistivity may be 6.2 ohm-cm to 10.2-ohm-cm.

Reaction terms

Matrix = copper

Electrode = graphite

0.5 Gd 1.0 Gd 2.0 CD 3.0 , CD 4.0 CD Example JU

Electrode cover = cotton gauze

Frequency = 9.85 kHz

At transfer speed = 1773 mm / minute

Application time = 2 minutes

Examination with the light and scanning microscope revealed a tin layer on the surface with a thickness of approximately 1.2 / um. The layer was uniformly thick and homogeneous. This is from Pig. 55 "

An SEM / KPMA scan of the interface resulted in a fusion of tin to a depth of at least 4 / um as can be seen from the table below and Figure 56 *.

Depth, / around element concentration (Massel)

i 1 sn 91.4 2 sn 4.4 3 sn 0.9 4 sn 0.5

Example ΣΧΓΙ

Ea, an aqueous solution of the following composition was prepared

Harness grams / liter

Z inn (U) chloride 9.4

Hatrium diphoaphate 44.7

Dextrin 6.25

Water (distilled) 1000 ml

Sodium lauryl sulfate 0.5

This solution had the following characteristic pH = 9.05

resistivity = 34 ohm-cm concentration of Sn = 0.50 mass

The pH can be varied between 9 and 9.7; the con-

+ 2

The concentration of Sn ions can be between 0.4 and 1 mass and the resistivity can be between 30 ohm-cm and 36 ohm-cm.

React ion d indungen

Matrix = copper

Electrode = graphite

Electrode cover = cotton gauze

Frequency = 9.85 kHz

Application speed = 1773 mm / minute

Application duration = 2 minutes

Examination with the light and Raatermikroakop revealed a tin layer on the surface with a thickness of approximately 4 / Um. This plot reveals a deeper uniform and substantially homogeneous layer approximately 1 μm thick and an outer slightly porous layer approximately 3 μm thick, as in Pig. 57 can be seen.

An SEM / EPMA scan of the interface revealed a fusion of tin to a depth of at least 5 / μm, as shown in the table below and FIG. 58.

Depth, / u m element concentration (mass)

97.3 94.3 1.0

An aqueous solution of the same composition as prepared for Example 2XEI would be used:

reaction conditions

Matrix = steel (ASA 1010)

Electrode = graphite

Electrode cover = cotton gauze

Frequency '= 10.61 kHz

Application speed = 1909.8 mm / minute

Application time = - 3 minutes

Examination with the light and scanning microscope revealed a tin layer on the surface with a thickness of over 2 / μm *

1 sn 2 sn 3 sn 5 sn Example iXEII

- 44 - L JD / i I ü

This layer was porous but continuous, as shown in Fig. 59.

An SEM / ΕΡΜΑ scan of the interface revealed a fusion of tin bia to a depth of at least 2 / μm, as shown in the table below and Pig. 60 can be seen »

Depth, / do element Massel

0.5 Sn 96.2

1.0 Sn 81.4

2.0 Sn 2.5

Example 23ZV

An aqueous solution with the following composition was prepared;

Έ grams / liter

Cobalt (II) sulfate 252

sodium fluoride 14

Boric acid 45

Dextrose 5

Sodium lauryl sulfate 0.2

Water (distilled) · 1000 ml

This solution had the following characteristics

pH = 6.03

resistivity = 28.5 ohm-cm

+2

Concentration of Co = 5 »3 mass

The pH can vary between 4 »5 and 6.5; the concentration

+2

The concentration of Co ions can be from 2 to 6 pigs and the resistivity can be between 25 ohm-cm and 30 ohm-cm.

reaction conditions

Matrix · = copper

Electrode = platinum

Electrode coating = Uylontüll

Prequency = 5 »1 kHz

Application speed = 918 mm / minute

Duration of application = 3 »O minutes

Examination with the light and Raatermikroskop revealed a Kobaltachicht on the surface with a thickness of approximately 6.5 / um. This layer is uniform and continuous, as shown in FIG. 61.

An SEM / ΕΡΜΑ scan of the interface showed a fusion of cobalt to a depth of at least 20 / μm, as shown in the table below and Pig'62.

Depth »/ around element concentration (Massel)

10 Co 2.65

15 Co 1.6

20 Co 0.87

25. Co 0.44

From the visual inspection and the preliminary experiments, it was found that the deposition of cobalt at a height of over 10 was extremely dense.

Example XXV

A viable solution having the following composition was prepared:

Name grams / liter

Silver cyanide 26

Potassium uranium 46

Potassium carbonate 37

sodium lauryl sulphate 1

Carbon disulfide 1-2

Water (distilled) 1000 ml

This solution had the following characteristics: pH = 11.55

specific resistance . = 10.5 ohm-cm concentration of Ag = 2.09 mass

The pH can be varied between 11.2 and 11.7; the concentration of Ag ions may be from 1 to 3 masses and the resistivity may be between 8 ohm-cm and 13 ohm-cm. "

- 46 - Z y D / I 1 U

React ionabe conditions

Matrix = copper

Electrode. = Platinum

Electrode coating = nylon

Frequency = 7> 7 kHz

On transmission time, it is 1386 mm / min

Application time = 1.0 minute

Exposure to the light and Raatermikroakop resulted in a silver layer on the surface with a thickness of approximately 5 / um. Daa structure is shown in FIGS. 63 and 63A.

An SEM / ΕΡΜΑ scan of the interface revealed silver oxide bia to a depth of at least 3 μm, as can be seen in the table below, and FIG.

Depth, / around element concentration (Massel)

98.7 91.4 46.3 2.4 T, 0

Ea an aqueous Lö'aung was prepared with the following composition :

Harness grams / liter

Silver nitrate 29

Potassium iodide 398

Citric acid 6

Dextroae 5

Carbon Dioxide 1.5

Ammonium hydroxide bia to pH

Waaaer (distilled) 1000 ml

This solution had the following characteristics j

pH = 5.6

specific resistance = 6.6 ohm-cm

'Ί

Concentration of Ag = 1.84 %

Ag 1 Ag 2 Ag 3 Ag 4 Ag 5 Beiapiel IXVl

- ^4? - 16 b / l ι

The pH can be varied between 1.5 and 2; the concentration of Ag ⁺ ions can be from 0.5 Ma to 2.5 mass and the specific resistance can be between 6 ohm-cm and ohm-cra,

React.ionabed indungen

Matrix = copper

Electrode = graphite

Electrode cover = cotton gauze

Frequency = 9.5 kHz

Application speed = 1710 mm / minute

Application duration. = 2.0 minutes

Scanning with the light and scanning microscope showed a silver layer on the surface with a thickness of approximately 2 / um. Daa microstructure is in Pig. 65 shown ·

An SEM / EPMA scan of the interface resulted in a fusion of silver to a depth of at least 2.00 / μm, as shown in the table below and Fig. 66.

Concentration (mass)

97.7 97.5 28.0 3.8 2.8 1.0

As apparent from the foregoing examples, the invention provides a novel process, apparatus for carrying out the process, solutions for use in the process, and novel products suitable for the most varied of applications and conditions of use.

When the description has been limited to examples in which the deposition on the entire surface was carried out, it is nevertheless to be noted that the application of course be limited to specific areas of surfaces, depending on a specific result required k s n *

Depth, - / um element 1 Ag 2 , Ag 3 Ag 4 Ag 5 Ag 6 Ag

-48- ZJb / 1 I U

For example, tin, gold and silver can be used as a result of the characteristic values of conductivity typical for electrical applications, and circuits can be melted onto other substrates. Also the anti-corrosion properties of tin, gold, silver, nickel, chromium Cadmium, molybdenum and tungsten are valuable, and the application of these metals to ferrous and non-ferrous substrates will improve their anti-corrosion behavior.

Chromium, nickel, silver, gold or tin also offer the possibility of giving the matrix a pleasant appearance. Chromium, molybdenum, tungsten, titanium and cobalt give the matrix surface hardness *

Indium adds strength to the matrix and also serves as an anti-chemical agent. A molybdenum-treated iron or non-iron matrix has improved friction wear and high temperature resistance characteristics. It is also suitable as a dielectric coating.

A cadmium-fused matrix not only has improved corrosion resistance characteristics but can also serve as an antifouling agent for the treatment of ship hulls »

Overall, silver-fused matrices are valuable as a reflective medium.

It will be apparent that the method and apparatus can be used in a very versatile manner without requiring much capital and equipment and allowing the use of materials in applications that previously were less costly than previously, and beyond the described applications and uses many others will be familiar to those skilled in the art.

It will also be apparent that the various parameters of the method may be varied according to the variables involved and the results sought, without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (12)

ο ό / \\ υ invention proposal; A method for fusing at least one second conductive chemical element having a matrix of a first conductive chemical element at ambient temperature, characterized in that the second conductive element is brought into contact with an adjacent surface of the first conductive chemical element, wherein the second conductive element is used in the form of a dissociable solution, and a chopped electrical signal of a certain frequency is applied to the first and second chemical elements, whereby the second chemical element is fused with the first chemical element * 2 «Method according to item 1, characterized in that the solution of the second chemical element is aqueous» 3 «method according to item 1, characterized in that the solution of the second chemical element is organic *. 4 * Method according to item 2, characterized in that the aqueous solution has a pH in the range of 0.4 to 14 and the second element in the solution in the range of 0.10 to 10 mass. »Is present. 5. Method according to item 4, characterized in that the solution has a resistivity in the range of 10 to 80 ohm-cm " 6, "method according to item 1, characterized in that the first conductive chemical element is selected from the group of iron and non-ferrous metals or an alloy thereof» 7. The method according to item 1, characterized in that the second conductive chemical element is selected from the group comprising iron and non-ferrous metals and their alloys. 8. The method according to item 6, characterized in that the first conductive element is selected from the non-ferrous metals or an alloy of the same comprehensive group » - * i - ι i b / ι ι A method according to item 5, characterized in that said first conductive element is selected from the group consisting of ferrous metals or an alloy thereof. 10. The method according to item 1, characterized in that the second conductive chemical element among the elements of the groups Tb, 2b, 3a, 4b, 6b, and 8 is selected, and the first conductive chemical elements of the iron or non-ferrous metals or a Alloy of the same comprehensive group is selected Product obtained by the method of item 1, characterized in that it has a matrix of a first conductive chemical element with an outer surface and a zone within the matrix on the outer surface of a second conductive element fused thereto the second conductive element is selected from the group comprising tin, indium, zinc, cadmium, copper, silver, gold, nickel, cobalt, iron or chromium. 12. Product characterized in that it has been produced by the method according to one of the preceding points. - For this 36 / Bl- drawings -