JPS61502710A - Heat-resistant coated articles - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Heat-resistant coated articles The present invention relates to articles formed from copper or copper alloys, particularly articles that can be exposed to high temperatures. Good regarding such items.

One area where the invention is particularly applicable is electrical wires and cables.

For example, used in electromagnetic windings of transformers, motors and pond devices. So-called "magnetic wires" are exposed to severe temperature changes under overload conditions during use.

Furthermore, in certain fields where cables are used, for example in the military or undersea, A cable that can function without damage for a certain period of time when exposed to fire It is preferable to use Rikimaru. Such cables may have circuit protection depending on their intended use. Also called full cable or signal integrity cable. Conventionally proposed circuit maintenance cables and signal integrity cables have their respective conductors resistant to fire exposure. By mica tape or large volume of filling material or silicone to prevent short circuits shall be separated from each other by or by a combination thereof. There is a principle, therefore, that traditional cables are quite heavy or large or heavy and big.

Wires and wires that function even at high temperatures with a thin insulating refractory coating (e.g. alumina) and Cables have been proposed. However, the inventors found that when the article was exposed to high temperatures Although the electrical properties of the fire-resistant coating are sufficient, the stability and integrity of the coating are poor. and found that the long-term use ability of the article can be severely reduced.

The present invention is an article of manufacture having at least a portion formed from metallic copper. hand, On the partial surface, there is provided an adhesive refractory layer substantially free of impurities and an oxygen-free layer. a metal that acts as a barrier to the diffusion of copper, copper, or both. the thickness of the intermediate layer is at least 1.1 μm, preferably the thickness is at least 1 μm; ．． 2 μm, more preferably at least 1.5 μm 1 Particularly preferably at least 2 μm μm 1 most preferably at least 3 μm.

In the article according to the invention, the metal forming the intermediate layer has a failure mechanism. Extends the life of the article at high temperatures by eliminating or substantially reducing it. I understand. i.e. in the case of circuits or signal integrity cables, for example, The time required to damage the circuit is substantially extended. inside for this purpose The metal forming the interlayer may be used to diffuse oxygen to the outer surface of the underlying substrate or to the spread of oxygen into the substrate. It is a metal that acts as a barrier against scattering. This may limit diffusion as an elemental form. or, in the case of aluminum, for example, when exposed to air to form oxide scales. diffusion can be hindered by Such scales are stable upon formation and It is most effective if the growth rate is small. Forms an alloy with the underlying substrate at high temperatures and A metal that is preferentially oxidized to form a stable scale when exposed to air. , or intermediate metal alloys with high oxidation stability (e.g. titano/aluminum alloys). can form layers. The metal forming the intermediate layer must have a physical or may also be selected to provide the best adhesion by utilizing chemical compatibility.

Additionally, supplying a relatively thick interlayer often makes the article mechanically abusive. It has also been found that crack formation in the refractory layer is significantly reduced in case. Less crack formation The reason for this is that when strain is applied to an article, the stress within the refractory layer is reduced due to the deformation of the intermediate layer. This is thought to be due to the change in the cloth. That is, according to another aspect, the present invention provides metal An article of manufacture having at least a portion formed of copper, the article comprising: on the partial surface, a cohesive refractory layer substantially free of impurities; Adhesive intermediate layer made of a metal with low modulus (e.g. aluminum) and the intermediate layer has a thickness of at least 1.1 μm. modular Since the absolute value of the The term modulus used in this book refers to an arbitrary value of one-layer strain of annealed lump material.

A single metal interlayer has a modulus less than copper and/or may act as a diffusion barrier to oxygen; in other cases, e.g. layer acts as a diffusion barrier and other layers act as stress relief or keying layers More than one intermediate layer may be provided, and so on. For example, a nickel item can be added to a copper item. Provides an intermediate diffusion barrier layer and over this nickel layer is an aluminum stress relief/key element. can provide a working layer.

When an article has more than one intermediate layer, the layers are typically differentiated to optimize properties. The intermediate layer can be relatively thin, and other requirements can be According to the invention, the present invention provides a manufacturing method having at least a portion formed from metallic copper. A close-contact electrical insulation product that is substantially free of impurities on the partial surface of the manufactured article. a fire-resistant layer, and at least two intermediate layers, the at least one intermediate layer comprising: Articles acting as diffusion barrier layers and/or strain relief layers and/or keying layers I will provide a. For example, at least one of the intermediate layers may include copper and/or oxygen. at least one other layer is a strain relief layer and/or a strain relief layer. can act as a keying layer.

As mentioned above, the refractory layer is substantially free of impurities, i.e., the refractory layer is substantially free of impurities. Contains only the intended substances to satisfy the intended function, and does not include substances produced in the manufacturing process. No. An important feature of the refractory layer is that the composition must be adjusted to optimize the high temperature performance of the article. It is a matter of good adjustment. Compositions include many mica-filled or glass-filled silicones as in the case of resin systems, are entirely inorganic and therefore cannot be used at normal or emergency high temperatures. No conversion occurs when subjected to use. The composition is combusted to form an inorganic insulation. eliminates the use of polymeric binders to support inorganic materials integrated by It can also be improved by Similarly, refractory coatings can be applied to electrochemical conversion of metal layers. Therefore, articles formed by, for example, electrodeposition of an aluminum layer are not covered by this invention. such layers usually contain ionic residues of the electrolyte, e.g. sulfuric acid electrodeposition. Heavily contaminated with sulfates from

Such wet chemical methods lead to contamination of the intermediate layer. Appropriate attachment method physical vapor deposition methods such as reactive evaporation and sputtering, or plasma There are assisted chemical vapor deposition methods. Plasma oxidation of metals or non-vacuum methods (e.g. high pressure CV A coating can also be formed by method D) and is fire resistant at temperatures not exceeding 350℃. Preferably, the layers are deposited.

The article of the present invention has a high resistance to high temperatures, and the integrity of the refractory coating is maintained even at high temperatures. It was found that it is not lost for a relatively long period of time. Articles of the invention and having an intermediate metal layer When an item that does not grow or does grow, but is thin, is examined by a scanning electron microscope. It has been observed that the failure mechanism of articles without an intermediate layer is mainly spalling. It was. Providing the article with a thicker metal interlayer reduces spalling and The copper migrates through the refractory layer and forms globules or "dykes" on the outer surface of the refractory layer. Appears to appear in the form of a J network or 'blister' Damage occurs in the mechanism. This form of failure occurs at temperatures such as 500°C, which is lower than the melting point of copper. It can occur even at low temperatures. The main reason why this failure occurs is not well understood, and more than one type It seems that various types of damage occur due to the above mechanism. One theory regarding the failure mechanism is that At high temperatures, by diffusion or by cracking (mechanical or thermal stress within the refractory layer) Oxygen in the air that enters the refractory layer from It is said that copper oxide (CutO or Cub) is formed, which is relatively conductive. That is true. Copper diffuses outward through copper oxide and combines with oxygen that diffuses inward. , the growth of copper oxide scale progresses until it reaches the outer surface of the refractory layer. circuit maintenance power In the case of wires, the electrical integrity of the system is greatly affected.

Whatever the exact failure mechanism, and if the underlying copper is or diffusion of oxygen or copper or both, whether in the form of oxides or This transition can be prevented by providing a relatively thick L) intermediate layer that acts as a barrier to It has been observed that the effects can be clearly reduced or prevented.

Thick interlayer reduces crack formation caused by thermal expansion mismatch between copper and refractory layer It has also been observed that the heat resistance of articles can be improved by preventing .

The article is an article having parts formed from bulk metallic copper, i.e. For example, it is preferable that the copper is not present only as a thin layer in close contact with the article. Delicious. For example, to protect copper from corrosion or to provide electrical insulation. The invention may be applied to any type of article provided with a refractory layer on top of a bulk copper substrate. . Examples of such articles include electrical connectors, mechanical couplings, and casings. There are many examples. The present invention is capable of functioning for a long period of time without damage even under high temperatures. Electrical items such as wires and cables (e.g. circuits and signal Particularly suitable for maintenance cables (as well as magnet wires). Hereinafter, the present invention will be described as and cables.

If the article comprises an electrical wire or cable, the underlying copper is the conductor of the cable. The conductor may be a single solid conductor, or 7.19 or individual strands to form a bundle preferably having 37 strands. It may also be a twisted conductor in which the lands are integrated. When twisting conductors, the individual strips The bundle rather than the trand is coated with an intermediate refractory layer, i.e. the intermediate refractory coating is substantially individual strands so that only the outer surface of the outermost strand is coated It spreads around the bundle rather than around the . Typically conventional tin or nickel coated strands such as conductors (however, in this case a tin or nickel coating is used in addition to the intermediate layer). ), it is possible to form twisted conductors from more than one metal.

This form of conductor maintains electrical contact between the strands and keeps bundle dimensions to a minimum. The thickness of the sag (vt covering) accounts for a significant proportion of the strand dimension in micro-dimension conductors. This is because ), most of the strand surface and the strands in the central area of the conductor Good electrical connection to conductors since all surfaces of the conductor are not covered by fire-resistant coating This has the advantage that the formation of (eg crimp connections) is facilitated.

In particular when forming circuits or signal integrity cables from stranded conductors according to the invention. Very flexible compared to other signal and circuit protection cables when using stranded conductors. It has the advantage of being flexible. Very tight bends (small bends and half) without harmful effects The possibility of bending the wires (diameter) provides an integrity layer for other signal and circuit Partly due to the fact that it is thinner than in cables. However, the conductor If it is a stranded conductor, it can be bent in extremely tight bends without undue stress on the surface of the strands. I can sing. The strands are arranged in regular hexagonal packing at the apex of the bend and are This is because the uncovered area of the strand is exposed to the eye. Electrical wire between adjacent stranded conductors, even if the uncoated conductor is exposed when the conductor is bent. No electrical contact occurs. In this case, the shape of the stranded conductor is not cylindrical but depends on the length of the conductor. It is a hexagonal shape that rotates along its length, and adjacent stranded conductors have several Since they contact each other only at points, integrity is maintained. These points are conductors In the outer layer of the It is. It is at these contact points that a fire-resistant coating is always applied.

The thickness of the refractory coating is at least 60,5, more preferably at least 1, especially less than 1. 271 m, preferably at most 15, especially at most 108 m. The most preferred thickness is approximately 5 Bm depending on the particular operating conditions. positive positive The exact thickness depends on many factors, including layer type and wire voltage rating, and All cables typically require somewhat thicker jacketing than signal integrity cables, approximately 15 μm or more. Sometimes it is above. The lower limit of the coating thickness is usually determined by the required voltage standard of the wire, On the other hand, the upper limit is usually determined by the time of the coating operation and therefore by the price.

Insulating refractory coating is an electrically insulating non-melting or refractory oxidation of a metal or metalloid Preferably, it is formed from a metal or a nitride. The present invention utilizes oxides or nitrides. Although a case is described, other coatings may be included.

The term "non-melting" or "refractory" means that the bulk coating material is Means not to melt or decompose when exposed to time. Oxide/or nitride It is preferable that the material can withstand even higher temperatures, for example, at a temperature of 1000°C It must be able to withstand at least 20 to 30 minutes. The preferred oxide is aluminum oxides of aluminum, titanium, tantalum and silicon, or mixtures thereof; or a mixture with other oxides.

Preferred nitrides are aluminum and silicon nitrides. Therefore, the present invention Also includes, for example, the use of mixed metal oxides for fire-resistant coatings. Oxide The nitride layer does not need to have a precise stoichiometry and often does not have a precise stoichiometry. It should be recognized that there is no stoichiometry. Often depends on the method of forming the refractory layer The coating then contains a stoichiometric excess of the metal or metalloid. That is, the coating contains more metal than is required for the stoichiometric equation of the oxidation state of the metal.

Therefore, "aluminum oxide", "titanium oxide", "tantalum oxide", "carbon oxide" "Iron", "metal oxide" and similarly corresponding nitrides refer to non-stoichiometric compounds. include. It may be advantageous for the refractory coating to be non-stoichiometric. to this This is because the adhesion between the fire-resistant coating and the underlying layer is improved, and the stress that occurs in the coating is reduced. so that the forces are not localized with the boundary 1 of the sheathing, e.g. due to differential thermal expansion, and The stoichiometry of the refractory coating is at least as large as its thickness so that different parts exhibit different properties. This is especially true when it changes in one part. For example, the coating is quite metal rich The solid part shows good adhesion to the conductor or intermediate layer, while the metal part of the coating or The part with the least amount of metalloids exhibits the best electrical properties.

In short, the stoichiometry of the refractory coating should vary continuously throughout the thickness of the coating. It may have one or more layers of very uniform stoichiometry. Therefore, the resistance The flammable coating is of fairly uniform stoichiometry, preferably with a high content of oxygen or nitrogen. It may have an outer region of , which exhibits optimal electrical properties. Heterogeneous and uniform layer phases The relative thickness may vary widely.

For example, a large portion of the coating may have a non-uniform stoichiometry, or a large portion of the coating may have a non-uniform stoichiometry. may have uniform chemistries. In the latter case, uneven areas of the coating are exposed to particularly high temperatures. It may be considered as an intermediate layer that improves the adhesion of the coating. underlying in sheathing When attempting to improve the adhesion of fire-resistant coatings with areas containing a large amount of metal or semi-metal. , whose specific composition depends on the composition of the underlying layers, in some cases metallic or semimetallic The portion enriched in preferably consists essentially entirely of a metal or metalloid. , gradually changes from a metal or metalloid to an oxide or nitride. This means that the system is Particular preference is given to the inclusion of an intermediate layer of a similar metal or metalloid.

The exact stoichiometry of the homogeneous top layer was determined using wavelength-dispersive electron microprobe analysis. or can be determined experimentally by using X-ray photoelectron spectroscopy (XPS). Wear. The composition of the coating, which changes from metallic to refractory throughout its depth, can be determined by compositional analysis. The film is continuously sputtered away to expose a new surface for It can be evaluated using Auger electron spectroscopy (AES).

Changes in stoichiometry are limited to changes in metal or metalloid/oxygen or nitrogen proportions. do not have. Additionally or alternatively, the relative proportions of two different metals or metalloids are For example, from one type of metal to an oxide or nitride of another metal making up the intermediate layer. It may change so that there is a gradual change.

The outer region of the refractory coating is free of oxygen or or at least 50% of the nitrogen molar content, more preferably at least 65%, especially Preferably it has an oxygen or nitrogen molar content of at least 80%. Therefore, The preferred oxide composition of the outer region is expressed by the formula: Ox [wherein X is at least 0.75 in the case of aluminum, preferably at least too! , in particular at least 1.25, and in the case of titanium or silicon at least I, preferably at least l3, especially at least I5, in the case of tantalum is at least i, 25, preferably at least 61.6, especially at least 2 . ].

Relatively thin refractory coatings with a stoichiometric excess of metals or metalloids are It maintains insulation properties when raised to a certain temperature (usually 300-600°C), and then heated to 30°C. It was found that when a load of V is applied, it becomes conductive.

Typically, the electrical properties of a coating are measured as the temperature at which it becomes conductive; improved both by thickening it and increasing its oxygen or nitrogen content (provided that the thickness or oxygen or nitrogen content may be increased).

At least in the broadest aspect of the invention, the fire-resistant coating is in close contact with the intermediate layer. may consist of only one layer; however, it is possible to form one or more additional layers. It is possible and often preferred to do so. For example, The refractory coating may have a refractory nitride layer thereon. improve mechanical properties Examples of nitrides that can be bonded to refractory soils include titanium nitride or aluminum nitride. Contains minium.

Other examples of additional layers that may be used are surface conductors and refractory oxide or nitride coatings. a refractory interlayer or another metal interlayer disposed between the two.

A metal interlayer adjacent to the refractory coating to improve adhesion between the refractory coating and the conductor. is preferably formed from a metal forming a refractory coating.

Preferred metal interlayers include nickel, aluminum, titanium, tantalum or oxide. Contains layers formed from ion, but other metals such as chromium, manganese or Silver may also be used.

If desired, more than one intermediate layer can be provided on the conductor. For example, during manufacturing or heating Can a barrier layer be provided between the conductor and other intermediate layers after processing or during high temperature use? , or alloy layers formed from deposited metals and conductive metals (e.g. aluminum/copper) It is possible. Coating, at least in some cases by providing an alloy layer Adhesion is significantly improved.

In the case of electrical equipment, a refractory layer may provide the total electrical insulation, or one layer or Further additional insulating layers can be provided thereon. Additional insulating stones can be inorganic or may be an organic layer or may provide a combination of inorganic and organic layers.

All compositions, structures and methods described herein may be applied to such articles. .

In the case of the wire of the invention, the polymer insulation provides additional insulation to the conductor during normal use conditions. properties, as well as desired dielectric and other properties (e.g. mechanical properties, abrasion resistance). It can also be supplied to give electric wires different characteristics (eg, polarity, color distribution, possibility, etc.). However, the original An important advantage of brightness is that a significant proportion or all of the used The electrical properties of polymer insulation mean that polymer insulation provides the only insulation between conductors. This is less important than in other wire structures being supplied. Electrical insulation Among the known polymer materials used for this purpose, polyethylene has the most suitable electrical properties. However, it is highly flammable and has poor mechanical properties. Flame retardant polyethylene 2 Attempts to address this issue have included hydrogen halides, which are corrosive and toxic when exposed to fire. halogenated flame retardants are required, or the electrical properties of the polymer and a fairly large amount of flame retardant, free of balogens that have a detrimental effect on mechanical properties. I need. Therefore, acceptable wires have traditionally been made from fairly thick-walled polymers. - often solved by using insulation and/or two-walled construction. It can only be obtained through a compromise between the different qualities that exist. Such forms of polymer insulation may be used in the wire of the present invention, but the presence of the refractory layer to a considerable extent Solve a problem. Polymers used for insulation sacrifice their electrical properties due to their flammability and This is because the material is selected in consideration of its properties and/or mechanical properties. polymer insulation Examples of polymers that may be used to form polyolefins, such as ethylene homopolymers and copolymers with α-olefins, halogenated polymers, e.g. For example, tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene, and vinyl chloride homo or copolymers, polyamides, polyesters, polyimides polyetherketones, such as polyaryletherketones, aromatic polyethers, Tellimides and sulfones, silicones, and alkene/vinyl acetate copolymers Examples include mar. Polymers may be used alone or in mixtures with each other. , fillers such as alcohol, metal oxides such as hydrated alumina and titania. Any treated or untreated metal oxide flame retardant may be included. Polymer has a single wall structure For example, a polyvinylidene fluoride layer may be made of polyvinylidene fluoride. It may be located above the polyethylene layer. Polymers do not have to be cross-linked, but can be mechanically For example, chemical cross-linking to reduce I5 and flow upon heating to improve physical properties. Preferably, the crosslinking is carried out by an agent or by electron beam or gamma irradiation. Yes. The polymer may be supplemented with other substances such as antioxidants, stabilizers, crosslinking promoters and It may also contain processing aids and the like. Polymer insulation prevents wires or cables from being exposed to fire. The filler, such that the filler of the polymeric insulation provides additional insulation when For example, hydrated alumina, hydrated titania, dawsonite and silica - among others. contain a filler having at least the same chemical composition as the refractory coating in the pyrolyzed state; Particularly preferred. The preferred type of polymer insulation in ponds is that it will charcoal when exposed to fire. ash, such as some of the aromatic polymers mentioned above, or ash, e.g. If exposed to fire, charcoal or ash will provide a fire-resistant coating. together with the necessary insulation.

Examples of polymers, their compositions, their manufacture and electrical wires using them are provided in U.S. Pat. ,269,862.3.580.829.3.953.400,3゜956.2 ．． 10.4.155.823.4, 121.001 and 4.320°224 , British Patent Specification Letter 1.473,972.1,603,205.2°068.3 47.2,035,333 and 1,604,405 and European Patent Specification Box 69,598. Wires must be virtually halogen-free. preferable.

The metal intermediate layer can be formed using various methods, such as electroplating, roll bonding, etc. Semi-conductor cladding method or coating with metal melt and vacuum evaporation method, e.g. Puttering, evaporation, thermal spraying, plasma assisted chemical vapor deposition (CVD) or other methods It may be formed by a method. Preferably, the intermediate layer is formed at a temperature not exceeding 150'C. do.

As mentioned above, any of the many ways to deposit a layer that is substantially free of impurities The refractory layer may be formed by either method. If desired, this layer can be removed by non-vacuum methods, e.g. It may be deposited by high pressure chemical vapor deposition.

However, vacuum deposition methods, e.g. evaporation, plasma-assisted chemical vapor deposition, especially sputtering The talling method is preferred.

In sputtering methods, primarily neutral atoms or molecular species are inert cations (e.g. argon ions) from the target that may be formed from released under bombardment. The released high-energy species can travel considerable distances. The wire conductor base is moved and maintained at medium vacuum (e.g. 10-' to 10-' mbar). Adheres to materials. The cations required for bombardment are generated when the sputtering target is Occurs in a glow discharge that acts as a cathode to a low discharge system. glow Negative potentials with respect to discharge and ground are applied to the cathode in the case of insulating target materials. It is maintained by using high frequency power, which is Keep the target surface on the target surface. If the target is a conductive material, apply DC power. may be used. The advantage of such a technique is that the control power of the target material is pleasantly increased. , the energy of the emitted species is e.g. Compared to evaporation method, sputtering method has 1-10 eV, which is much higher than evaporation method. Ru. Although considerable improvements in interfacial bonding can be achieved, the addition of the sputtering method described The deposition rate is lower than that of electron beam evaporation.

In the magnetron sputtering method, plasma is connected to the cathode (target) by a magnetic field. It is concentrated just before the (cut). The effect of magnetic fields on gas discharges is dramatic. After the cathode Permanent magnets, which are usually placed in In the discharge region 1, the secondary electrons generated from the sputter bombardment process are Deflected into a circular or helical path by force. Therefore, the electron density at the cathode surface is and the number of ionized argon atoms bombarding the cathode is substantially increased. P There is an increase in plasma density and a significant increase in deposition rate. bahia Sputtering (sputter ion plating) may be used as a variation of this technique. stomach.

In this case, the wire conductor is kept at a negative potential with respect to the chamber and the plasma. . Bombardment of wire conductors with argon ions creates an extremely clean surface. Jiru. The sputtering of the target material onto the wire conductor in this process A simultaneous wear/clean mechanism occurs. This is said to significantly improve interfacial bonding. has advantages. In sputter ion plating systems, both substrate and wire conductors are The other is kept at a negative potential.

In this case, the relative potentials promote preferential sputtering of the target material It's balanced like that. Target voltage depends on system design and target material. Typically smaller than IKV depending. The wire base material is lower than the target. It may be exposed to its own polar plasma depending on the bias potential. target or the exact voltage/power relationship achieved at the substrate depends on many variables; The details differ from system to system. The typical power density on the target is l O~20W/ax'. The load on the substrate may be substantially lower and the target This is frequently as low as 5% of the load.

The preferred technique used to apply the oxide or nitride coating is via reactive vias. This is a sputtering method. In this method, in this case the oxide/nitride The oxide/nitride of the target material, which is a metal or metalloid, is attached. Add reactive gas to the vacuum chamber in addition to Rougone.

-Introduce within. The experimental results show that the level of reactive gas and its introduction rate are It has been found to have a significant impact on speed. Control of reactive gas partial pressure and Analysis of sputtering atmospheres in closed loop control systems is highly desirable. the above In addition to the simultaneous deposition/cleaning benefits of The coating is more fully formed to achieve the required stoichiometry as it increases surface reactions between the species. to be accomplished.

The partial pressure of the reactive gas is determined experimentally, but is usually 2-25%, up to 30%. Sometimes it is. The exact value depends on the coating chemistry and deposition rate. . Reactive sputtering is the preferred technique as it facilitates changes in the stoichiometry of the coating. It is. For example, the pure metal intermediate "layer" used for oxide/nitride coatings is No sharp boundaries between conductive metal, metal oxide/nitride and oxide/nitride layers It can be attached like this.

Various targets and microprocessor gas controls used in these methods Ancillary equipment including units and vacuum chambers are commercially available. Many in design Many variations are possible, but for use with any of the above vacuum deposition methods, the Most often use a “box” shaped chamber that can reduce the pressure to a high vacuum. Ru. The system is typically, but not exclusively, subjected to multiple attachment methods. Coating the wire One system that may be used to do this involves passing electrical wire conductors through a deposition chamber. either side of the main deposition chamber using air-to-air transfer techniques for using one or more auxiliary vacuum chambers.

These auxiliary chambers are connected to the atmosphere from the deposition chamber and are The pressure is kept at a higher level. This reduces the load on individual vacuum seals. explanation System 1 has the advantage of continuously supplying wire conductors to batch processing equipment. have In a vacuum deposition chamber, the pressure is typically between 10-’ and 10-” Torr. Preferably, the pressure is kept constant.

The target used is a commercially available planar-magnetron sputtering source. child These dimensions are not limited, and targets with lengths greater than 21 may be used. 2~ Four such sources surround or surround the electrical wire conductor passing through the chamber. They may be placed opposite each other so as to sputter from at least two sides.

The devices may be used in series to increase wire processing speed. As mentioned above, Apply a negative bias to the magnetron to begin the taring process. Above The wire may be kept at a low negative bias.

Improvements to the system may be made if necessary. For example, the atmosphere (population side) and vapor deposition vacuum deposition chamber by using an intermediate vacuum station between the chambers. The surface of the wire conductor is cleaned by ion bombardment before entering the bar, and the wire conductor is heated. Generates an argon ion glow discharge that also heats.

Additionally, to deposit the intermediate layer, the intermediate chamber is cleaned in a cleaning chamber and a deposition chamber. May be used between bars.

Conditions may be controlled to produce the above conductor coating without sharp boundaries between layers. . For example, an intermediate "layer" of pure metal used for a fire-resistant coating may be a conductive metal, an intermediate It can be deposited so that there are no sharp boundaries between the layers and the oxide or nitride coating.

Similarly, additional chambers can be refractory for improved lubrication or wear resistance. Deposition chambers for depositing different metals, metal oxides or metal alloys on top of chemical coatings. It may be used between the chamber and the atmosphere (outlet side).

Very advantageous adhesion due to evaporation and related methods of ion plating and active evaporation Another technique is available that allows the coating to be deposited at high speed.

Evaporation of the coating material involves heating the material so that its vapor pressure exceeds to-'' millibar. Do by doing. The evaporation temperature varies depending on the coating material, e.g. (1300-1800°C for metal oxides), the chamber pressure is usually 10-4~ 1 O-(N mbar).A similar wire transfer system as described would be approximately 3 It may be used to maintain the base temperature between 0 and 40 CJI. Some heating methods, e.g. There are anti-responsive, inductive, and electron hem inbinnoment types. But preferred The method involves a high-energy (e.g. IO,000eV) electron beam being placed in a water-cooled melt. An electron beam source that impinges on the coating material in the tank. Multi-pot crucible or twi By using a source gun, with the help of electronic monitors and controls It becomes possible to deposit multiple layers and chemical gradient layers.

Compound coating is the direct coating of the compound (e.g. AQtO*). by evaporation or by reactive evaporation (on partial pressure of oxygen to give aluminum oxide) (evaporated aluminum). Changes in method are reactive or For example, activated reactive evaporation (ARE) It can be used to increase the possibility of reaction between the starting material and the reactive gas.

In ion plating, a negative bias applied to the substrate in an inert gas The second cleaning/adhesion simultaneous mechanism explains how to optimize adhesion by using the uttering method. promote ism. A bias level of -2KV is typically used; Can be reduced as appropriate for the material. Alternatively, a high bias level can be used to achieve similar effects. Can be applied to a plate placed behind the traverse wire to achieve this. ion The operating pressure in the plating method is high (e.g. 1O""3 to 1O--libar), so , a more uniform coating is formed. Ion plating method is used to protect the filament. The electron beam gun is differentially pumped to maintain a vacuum higher than 10-1 libar. adjusted.

In the plasma assisted chemical vapor deposition (PACVD) process, the substrate to be coated is coated with a suitable gas. exposed to a low pressure (0.1-10 torr) plasma of gas/volatile compounds. this pressure The power is determined by balancing the overall gas flow rate against the throughput of the pump system. It is maintained. Plasma is electrically activated and connected from a power source through an adapted network. It is preserved by coupling the energy to the gaseous medium. thin film has been successfully deposited from high frequency plasmas into the DC and microwave regions. Ru. At high frequencies, energy depends on chamber design and electrode geometry. May be coupled capacitively or inductively. Typically, capacitively coupled enables power densities of 0.1-10 W/C in parallel plate reactors. A standard 13.56 MHz high frequency generator may be used. The base material can be heated up to 400℃. Can be set to a temperature of May float. Typically, the deposition rate with this technique is higher than that achieved with sputtering. It is convenient to compare the deposition rate with

Alumina deposition can occur under appropriate processing conditions in the presence of oxygen and volatile aluminum compounds ( (e.g. trimethylaluminum or aluminum butoxide) This may be done by exposing the substrate to a matrix.

After applying the oxide coating to the wire conductor, the polymer insulation is applied as is well known in the art. It may be extruded onto a coated conductor by a method similar to that described above.

To form a circuit or signal integrity cable, suitable electrical wires of the invention are simply assembled. It is enclosed in a jacket. If necessary, before applying the cable jacket, Wires may be provided with screens or electromagnetic shielding. The cable is In a well-known continuous process, a wire bundle is braided and a cable jacket is placed on top of it. It can be formed by extrusion. Using any of the above materials for wire polymer insulation However, halogen-free compositions, such as the above-mentioned British Patent Specification Letter 1,603,2 Preference is given to the compositions described in No. 05 and No. 2068.347A. cloud Additional measures may be used to provide cable integrity, such as wrapping with backing tape. Although possible, these are not necessary and would increase the size and weight of the cable. undesirable from the viewpoint of adding

The oxide layer is coated with a polymeric resin to provide a barrier to water or electrolyte during use. Alternatively, it may be desirable to cover with a thin coat of lacquer.

The present invention provides a method for forming flat cables that cannot be wrapped with mica tape. Particularly suitable for

Below, some embodiments of the present invention and manufacturing methods thereof will be shown with reference to the accompanying drawings. The invention is not limited to these embodiments.

FIG. 1 is a sectional view of one embodiment of the electric wire of the present invention, and FIG. 2 is a cross-sectional view of an embodiment of the electric wire of the present invention. Figure 3 is a cross-sectional view of a part of the conductor flat cable. Figure 1 shows a part of the wire handling mechanism. Schematic diagram of 5 and 6 are schematic cross-sectional views of a portion of the article of the present invention in the thickness direction, FIG. 7 is a graph showing the improved crack resistance of articles of the present invention.

In Figure 1, a 26AWG stranded copper conductor formed from 19 copper strands l. is coated with an aluminum oxide layer 2 with a thickness of 5 μm by the sputter ion plating method described above. It's been overturned. The outer surface of the twisted conductor has a thickness of 3 μm on which aluminum oxide is attached. m of aluminum layer (not shown). Trade name “Ultem (UL) Polyetherimide or polyether ether commercially available as TEM) J A terketone or polyether ketone based coating 3 is pressed onto the oxide coated conductor. The material is exposed to form a polymer "insulating" layer with an average thickness of 02 vrm.

Figure 2 is described in Example IA of British Patent Specification Letter No. 2,068,347. The seven electric wires shown in Figure 1 are bundled together, and the electromagnetic wave shielding is applied around the bundle by braiding. A jacket 5 based on a halogen-free composition is pressed onto it. The signal integrity cable formed by the cable is shown.

Cables so formed have a fairly small overall diameter relative to the volume of the copper conductor. It is particularly lightweight.

Figure 3 shows a row of flat copper conductors l spaced 100 mils (2,543 IJI) apart. A flat cable with a flat conductor is shown. Each copper conductor l has a thickness as described above. A 3 μm aluminum intermediate layer and a 5 μm thick alumina layer above it were provided. ing. The coated conductor may be made of, for example, polyether commercially available under the trade name ``Ultem''. Shaped from tellimide or polyetheretherketone or polyetherketone embedded in a single polymer insulation layer.

The apparatus used in batch processing to coat wire conductor substrates is shown in FIG. child In this device, a complete wire moving mechanism operates a wire draw-out reel 2 and a take-up reel 3. a vacuum chamber containing a wire support roll lO and a tension roll 1; 1 is provided. The mechanism connects a vertically installed target 5 with an electric wire. A motor is driven to control the passage of the electric wire 4 so that the electric wire 4 crosses the electric wire many times. Adhesion is , resulting from the above processing. As mentioned above, changes can be made with equipment. coating Using an additional target (not shown) on the other side of the wire to increase the speed Often additional targets, e.g. target 6, are used to deposit the primary oxide/nitride coating. It can be used to deposit intermediate layers before and/or after. The specific geometry used The design of the proper gas inlet system to fit what is clear as above Deposition of layers without boundaries is facilitated. Batch length depends on chamber dimensions and movement Depends on system design.

In such batch processing operations, the electrical wires 4. is one hole 2 in the chamber Move to the other reel 3. Depending on the route the wire takes, the wire can be made of any desired material. A small auxiliary target 6 may be passed through to deposit the intermediate layer of material. Ta for this target combined with the number of passes through the target and the wire speed. The interlayer deposition thickness can be controlled by the power applied. Next, wire 4 is a large main target. 5, and the main coating is deposited. The thickness is determined by the electric wire speed and number of passes. Determined by The ratio of intermediate layer to primary coating thickness is similarly controlled. Multilayer is , the mechanism is preferably such that the wire 4 passes through the target 5.6 in reverse order. It can be formed by reversing it. Thickness and composition can be reversed as required. It's okay to change. For example, the process used in small magnetrons is , for example, to deposit metal compounds on Ti and TiNx. It may be responsive. Clear between metal interlayer (or substrate) and oxide/nitride coating Deposition of layers without boundaries is targeted at deposition in an argon-rich atmosphere. 5 to the upper end of the wire, and the reactive gas is released as the wire lowers down the target surface. Set up a reactive gas gradient in the plane of the main target so that the content gradually increases This can be done by: The gradient is the acid introduced at the lower end of the target. obtained by a baffle system (not shown) that gradually leaks the element toward the upper end. be able to.

A simple way to form layers without sharp boundaries is to run wires 4 through the system. Pass back and forth to ensure that reactive gas levels obtain accurate stoichiometry on each pass. This includes the use of multiple passes to increase the final level required to achieve the desired results. Therefore, The chemical theory of the intermediate layer is as a series of small incremental steps from the metal to the required stoichiometry. increases. Use of composite targets to form interlayers with chemical gradients It's okay to stay. For separated articles, the article can alternatively be targeted by a rotating sample holder. May be held in front of the cut.

Figures 5 and 6 illustrate the present invention showing typical arrangements of layers that may be formed on a copper substrate. 1 is a schematic cross-sectional view of a portion of a bright article; FIG. The layer thickness is enlarged for clarity. Ru.

As shown in FIG. A copper substrate 1 is provided with an aluminum metal layer 2 having a thickness of approximately 2 to IO μm. acid Aluminum oxide A Q 20 x (where X is adjacent to the aluminum layer It varies from 0 in the area to 3 in the upper surface. ) Layer 3 is supplied on top of the aluminum layer A thin layer 4 (e.g. about 3 μm thick) of chemical aluminum oxide is deposited on the aluminum oxide. It is attached to the upper surface of the mu layer. Additional titanium nitride thin to increase the toughness of the article Layer 5 may be applied, followed by a relatively thick organic polymer layer 6.

Although the sound is clearly demarcated by lines in the drawings, such boundaries are , / aluminum, aluminum / A Qz OX and A Q t Ox /, 〇, 03 layers in particular do not actually need to be formed, which is preferable. That's a good thing. In fact, aluminum, AQtOX and stoichiometric The Mina layers may all be formed by the same sputtering process, in which case the layer Stoichiometry depends on the oxygen gradient used.

Another typical example is shown in FIG. In FIG. 6, the copper base material 21 has a thickness of (for example, 1 to 3 μm) nickel layer 22, metal aluminum layer 23, non-chemical m stoichiometric aluminum oxide Arbox layer 24 and stoichiometric aluminum oxide A ( ! There are 25 TOS layers. Layers 23, 24 and 25 are sputtered It is formed by Additional, fairly thick (e.g. approximately 5-15 μm thick) An aluminum oxide layer 26 may be deposited over layer 2.5 by non-vacuum deposition methods.

Examples are shown below.

Examples 1-7 By using the sputtering apparatus schematically shown in Fig. 4, various thicknesses can be formed. A aluminum interlayer was applied to the copper conductor. The sputtering conditions are as follows.

The wires were cleaned by vapor degreasing in 1.1.1-trichloroethane before deposition. Cleaned beforehand. Cleaning is carried out by continuously placing the wire in a steam degreasing bath with a residence time of 3 minutes. This was done by passing it through.

As shown in FIG. 4, the electric wire 4 was placed in a vacuum chamber. before starting the process. The chamber was evacuated to 1×10-L mbar. At this stage, argon is introduced and pressure is A force of 1.5 x lO-' mbar was applied. Here, a high frequency (80KHz) bias voltage is applied. The proposed method was applied to a wire handling system insulated from ground. Bias potential - Set the voltage to 850V and connect the wire 4 from reel 2 to reel 3 so that the residence time is 10 minutes. was moved. After completing the cleaning cycle, reduce the pressure to 8 to 10-’mbar Then, the adhesion process started.

A DC power of 3 KW was applied to the aluminum target 5. The wire starts from reel 2 It moved to reel 3 and was coated as it passed target 5. Stagnation in this area The residence time was adjusted by wire speed to obtain the required thickness.

The roll mechanism allows you to be exposed to one target as you pass the target. The surface of the wire that is exposed has changed.

A sample of copper conductor coated with aluminum was then subjected to the same treatment as described above. coated with aluminum oxide. Because of this second coating, the aluminum oxide target The kit was powered by an RF Ti source.

Aluminum oxide with a constant thickness of approximately 4 μm for wire residence time and target power Adjusted to obtain. Deposition of both aluminum and aluminum oxide Sometimes, the copper conductor was held at an appropriate bias potential with respect to the chamber to promote adhesion. . The measured DC dielectric strength of the refractory aluminum oxide layer was 57v/μm .

Twist a pair of similar wires (length 2, 2 twists per 5 am), twist a pair Form the cable and connect one end of the wire to an IMHz, 30V square wave generator, Observe the waveform at the other end of the line with a 200 ohm load using an oscilloscope. The electrical performance of the insulated wire thus formed was tested. 8cm wide flat The twisted pair cable was heated by a propane gas burner with a flame. screw The flame temperature directly below the pair was maintained at 900°C, and the time until failure was recorded.

The results are shown in Table 1. According to Table 1, an intermediate layer is provided under the fire-resistant coating of the present invention. It can be seen that it takes longer for the double line to break.

Table 1 Example Aluminum Thickness of propane intermediate layer at 900℃ Until damage due to flame Time (μm) (minutes) 6 6.2 94 7 II 360* *The test was completed without observing any damage even after 360 minutes.

After completing the propane flame test, the torsion-paired specimen was examined using an optical microscope and a scanning electron microscope. I observed it. As stated in the specification, if the intermediate layer is thick, copper may migrate and oxidize. The damage was caused by the formation of copper oxide. However, as the thickness of the intermediate layer increases , the cracks around the aluminum oxide are undetectable even at 200x magnification. Diminished. This reduction in crack formation is due to the fact that the aluminum interlayer is more oxidized than copper. This is surprising considering the fact that the thermal expansion mismatch with aluminum is high. be. In such cases, the transition may be accomplished by low-velocity diffusion within the fire shield or by wire strands. The disease progressed through inter-domain diffusion. Such gradual changes in failure are not observed. This was reflected in the time to destruction.

Example 8 A 7 strand 20 AWG conductor with a first layer that is a 2 μm thick titanium layer, approximately 2 μm thick. a second layer which is a μm gradient stoichiometry Ti0x (where X is 0 to 2) layer and A composite coating was provided consisting of a third layer, a 2 μm thick Tidy layer.

The composite coating is spun with low-density polyurethane using reactive sputtering methods and equipment as previously described. An insulating layer of ethylene (0.25 mm thick) was applied to the coated conductor.

These twisted pairs of coated conductors were heated to 900° C. for 10 seconds. polymer insulation Even after burnout, the coating remains intact, with no spalling or interlayer copper migration. It was observed that there was no

Example 9 A composite coating consisting of an intermediate layer varying from metal to TatO5 was provided. Titanta As described in Example 8, except that the target was replaced with a tankle target. Manufactured in The thickness of the metal intermediate layer is 1.1 μm, and the total thickness of the intermediate layer and upper layer is 2 ．． It was 3 μm.

The DC resistivity of the sample before exposing it to a Bunsen burner flame at 900°C for 30 seconds is 2. 5X10"Ω・cm.The DC resistivity after cooling was 1.3XI012Ω・am Met. Samples were also observed by scanning electron microscopy. Spalling et al. No lines were observed. .

Sudir mass heated with a cartridge heater and forming one electrode of the measuring circuit , and a probe of known contact surfaces forming the other electrode. The volume resistivity at the bottom was also measured. Grounded Faraday Cage The parts were housed in a cage. The heating rate of the mass is not constant, approximately 25°C/min. Heating was carried out at a rate of about 400°C and then reduced to a constant rate to about IO°C.

The limit of the device was approximately 650°C. Avo Ltd, Dorper, UK Test voltage 3 using a megohmmeter manufactured by Volume resistivity was measured at 0V (DC).

Using this device, we were able to measure volume resistivity at small temperature intervals, so conductor insulation was The temperature at which it is no longer possible to maintain 30V (the curve becomes almost flat by this temperature) It was possible to measure the The failure temperature was 485°C.

Examples 10-13 19 strand 22 AWG wire samples were coated with various thicknesses of aluminum as described in Examples 1-7. A aluminum interlayer was applied followed by a 4 μm thick aluminum oxide layer.

The sample was suspended in air with a slight spring tension applied at 45 second intervals for a duration of 60 seconds. The test was conducted by repeatedly passing square wave 36A current pulses of . This results in A cycle was performed in which the temperature of the sample rose to about 750°C and returned to the original temperature. this Observation of the sample under an optical microscope during cycling showed the formation of copper oxide.

The results are shown in Table 2.

Example Aluminum Intermediate layer thickness Notes (μm) Slightly oxidized after 10 (comparative) II cycles Moderately oxidized after 2 cycles object formation Large oxide formed after 3 cycles 11 3 Slight oxide formation after 2 cycles Moderate oxide formation after 4 cycles Growth +2 After 12 and 14 cycles, a slight oxide was formed.The test ended after 50 cycles. However, only a small amount of oxide was formed.

13 3* Slight oxide formation after 100 cycles * This sample contains copper and Between the aluminum there was an additional 1 μm thick nickel layer.

This result indicates that increasing the thickness of the interlayer increases the oxidation resistance of the substrate and It is shown that further improvement can be achieved by supplying a nickel layer.

Examples 14 and 15 A high tensile strain was applied to the wire samples manufactured in Examples 11 and 12, and the surface oxidized aluminum was Crack formation in the aluminum layer was observed. The results are shown in Figure 7 as a graph. Distortion? As the strain increases, the strain (shown on the horizontal axis) increases, and the crack spacing, shown on the vertical axis, decreases.

Regardless of the degree of strain, samples with a 12 μm thick aluminum intermediate layer (Example 1) The number of cracks in 2) is the same as that of the sample having an aluminum intermediate layer with a thickness of 3 μm (Example 11). The number of cracks was found to be much smaller than that of Decrease in crack density tensile specimen This shows that the detailed stress distribution within the refractory layer changes when This means that the mechanical shows important features in reducing spalling during overuse.

Examples 16-18 A 19 strand 22 AWG copper conductor conductive sample was prepared using aluminum as described in Examples 1-7. It was coated with an intermediate layer and then with refractory aluminum nitride.

The refractory nitride layer was heated in an argon/nitrogen atmosphere at a total pressure of 8 x 10-3 mbar. , deposited by reactive sputtering from an aluminum target. chemical quantity Keep nitrogen flowing into the chamber so that the aluminum nitride adheres to the conductor. I held it. The wire residence time and target power should be adjusted with a refractory nitride coating thickness of approx. It was adjusted so that it was μm. The thickness of the aluminum intermediate layer is as shown in Table 3. It was various.

The dielectric strength of the refractory aluminum nitride layer was 108 V/μm.

The high temperature electrical performance of the insulated wires was tested as described in Examples 1-7.

The results are shown in Table 3. Electrical wires provided with a metal interlayer under a refractory nitride coating are It can be seen that it works better at higher temperatures.

The test samples were observed under an optical microscope. Samples with thick aluminum interlayer (conducted example! 7) appeared to be in good condition with no peripheral cracks in the nitride layer. middle The sample without the layer (Example 16) was severely cracked and had spores from the copper conductor. ng was occurring.

Intermediate layer thickness Time until damage due to flame 17 +0 90 18 3* 39 *This sample has a gradient chemistry between the aluminum interlayer and the refractory nitride layer. I was in the middle class. Stoichiometry ranges from metallic aluminum to aluminum nitride There was a smooth transition, and the total thickness of the gradient layer and stoichiometric nitride layer was about 2 μm. .

Examples I9 and 20 3.5μm thick refractory aluminum oxide coating with 19 strands 22AWG copper It was supplied onto the wire conductor by sputtering. Some of the conductors have a thickness of 3 A .mu.m aluminum intermediate layer had been supplied. The adhesion between the fireproof layer and the underlying metal is The evaluation was made by observing the sample under an optical microscope while pulling it. A certain level of When strain is applied, the adhesion of the refractory layer reaches its limit and the spalling from the keying below A problem occurs. The strain at this time was measured. The results are shown in Table 4. fireproof layer and gold underneath It turns out that it is possible to choose an intermediate layer that significantly increases the adhesion with the genus.

Although spalling occurs in the fire-resistant layer of Example 19 even when handled gently, spalling occurs in the fire-resistant layer of Example 20. The layer was found to withstand mechanical abuse without spalling. Table 4 Example aluminum spalling Distortion at intermediate fz thickness (μm) (%) +9 (comparison) 0 1.6 A 19 strand 22 AWG copper wire conductor sample was prepared with R from a silicon dioxide target. It was coated with a 5 μm thick refractory layer of silicon dioxide by F sputtering. go In some cases, the refractory layer is applied directly to the copper conductor, and in some cases, the thickness is applied to the wire. A 10 μm aluminum interlayer was provided and produced as described in Examples 1-7. . The high temperature electrical performance of twisted pairs of these wires was tested as described below. Results first It is shown in Table 5. According to Table 5, an electric wire with a metal intermediate layer is an electric wire without an intermediate layer. It can be seen that it works much better than. After the test, the wire was observed again under the microscope. Ta. The fire-resistant layer of Example 2+ (without interlayer) had severe cracks and sporks. A ring had formed, but the fire-resistant layer of Example 22 (with aluminum interlayer) No cracks or spalling were observed. The breakage is caused by copper oxidation between the strands. This happened due to rapid growth.

back i front Example Aluminum Thickness of propane intermediate layer at 900℃ Until damage due to flame Time (μm) (minutes) 21 (comparison) 01 Example 23 The thickness of the aluminum intermediate layer was 10 μm, and the thickness of the aluminum intermediate layer was 0.25 mm. Supplying cross-linked polyethylene/ethylene vinyl acetate copolymer blend insulation to electrical wires Example 7 was repeated with the following exceptions. The wire is propane with a nominal temperature of 900℃ It took 113 minutes before it was destroyed by the flames.

This temperature takes into account only the unregulated temperature rise that would cause the wire's polymer insulation to ignite. It is given as a nominal temperature.

Examples 24 and 25 A flat copper conductor sample was sputter coated with 2 μm thick chromium, then coated with 2 μm thick chromium. Aluminum oxide was sputter coated. For comparison, a flat conductor (chromium intermediate layer) ) was also sputter coated with 2 μm thick aluminum oxide. Insulated conductor Test high temperature integrity by heating the body to 800°C for 10 minutes (in air) did. The samples were then observed under an optical microscope.

The sample with chromium interlayer (Example 24) was completely intact and undamaged (stainless). Neither poling nor oxidized steel growth was observed). In contrast, it has no middle layer The sample (Example 25) was in very poor condition. aluminum oxide film Completely gone, the copper conductor is a thick 19 strand 22AWG copper with copper oxide scale. For electrical wire conductors, the wires listed in Table 6 extend around the bundle rather than around the individual strands. A nickel intermediate layer was sputter coated to a thickness of Next, those described in Examples 1 to 7 A 4 μm thick aluminum oxide refractory layer was sputter coated using a method.

The high temperature electrical performance of the absolute HTi wires was tested as described in Examples 1-7.

The results are shown in Table 6. According to Table 6, the nickel intermediate layer of the invention (particularly thick one) It can be seen that this significantly improves the high temperature performance of the wire.

Table 6 Example Nickel Thickness of propane intermediate layer at 900℃ Time until damage due to flame (m) (minutes) l(comparison)OO,2 261,56 international search report AZJNEX To Tl4E IIITER) IATIONAL 5EARC 4 (R3?ORT ON

Claims (21)

[Claims] 1. An article of manufacture having at least a portion formed from metallic copper, the article comprising: On said partial surface is a substantially impurity-free adhesive electrically insulating refractory layer, and also oxygen. formed from a metal that acts as a barrier to diffusion of copper or copper or both. The intermediate layer is designed to suppress the migration of copper to the refractory layer when the article is heated. Article having a thickness of at least 1.1 μm. 2. An article of manufacture having at least a portion formed from metallic copper, the article comprising: a substantially impurity-free cohesive refractory layer on the partial surface, and a layer more modulus than copper. It has an adhesive intermediate layer made of metal with small lath, and the thickness of the intermediate layer is small. Both are 1.1 μm. 3. The thickness of the intermediate layer is at least 1.5 μm, preferably at least 2.0 μm. An article according to claim 1 or 2. 4. Claims 1 to 3, wherein the refractory layer comprises a metal oxide or metal nitride. Articles listed in any of the above. 5. The refractory layer is formed by a vacuum deposition method, preferably a sputter plating method. The article according to any one of claims 1 to 4. 6. The intermediate layer is formed by vacuum evaporation, preferably sputter plating or metal rolling. A seal formed by a coating method or electroplating method or a metal melt coating. The article according to any one of Items 1 to 5. 7. Intermediate layer is aluminum, silicon, titanium, tantalum, nickel, manganese , chromium or an alloy thereof. Articles described in Crab. 8. The refractory layer comprises an inorganic metal compound, and the intermediate layer comprises gold present in the refractory layer. 8. An article according to any one of claims 1 to 7, comprising a metal of the same genus. 9. The intermediate layer is formed from a metal that forms an intermetallic compound or solid solution with the copper when heated The article according to any one of claims 1 to 8. 10. Claims 1 to 9, wherein the intermediate layer comprises aluminum or nickel. Articles listed in any of the above. 11. The refractory layer is made of aluminum, silicon, titanium or tantalum oxides or or a nitride of silicon or aluminum. Items listed. 12. The thickness of the refractory layer is at least 1 μm, preferably at least 2 μm, more Preferably at least 5 μm, especially at least 10 μm. The article according to any one of items 1 to 11. 13. The stoichiometry of a refractory layer is the ratio of the metal or metalloid in the layer toward the outer surface of the layer. a claim that varies in at least a portion of its thickness such that it once decreases; The article according to any one of items 1 to 12. 14. The stoichiometry of the refractory layer is such that no sharp boundary exists between the intermediate layer and the refractory layer. 14. The article of claim 13 which varies as described above. 15. Claim 1 having one or more additional layers on top of the fireproof layer The article according to any one of items 1 to 14. 16. The product according to any one of claims 1 to 15, having two or more intermediate layers. Goods. 17. An article of manufacture having at least a portion formed from metallic copper, the article comprising: a substantially impurity-free deposited electrically insulating refractory layer on said partial surface; Both have two intermediate layers, at least one of which has a diffusion barrier and/or strain. Articles that act as removal and/or keying layers. 18. At least one of the intermediate layers acts as a barrier to copper and/or oxygen diffusion. the intermediate layer or at least one other intermediate layer acts as a strain relief layer and/or 18. Article according to claim 16 or 17, which acts as a keying layer. 19. The article according to any one of claims 1 to 18, which is in the form of an electric wire. 20. Article according to claim 19, wherein an additional outer polymeric insulation is provided. . 21. The refractory layer protects the underlying copper from corrosion according to claims 1 to 18. Goods.