MXPA97010122A - Lubrication in me work - Google Patents

Abstract

Process for working refractory metals and other metals using a lubricant comprising perfluorocarbon compounds (PFCs), including aliphatic perfluorocarbon compounds (-PFCs) having the general formula: CnF2n + 2, perfluromorfolins having the general formula CnF2n + 1ON, perfluoromines (PFAs) and highly fluorinated amines (HFAs), and perfluoroeters (PFEs) and highly fluorinated ethers (HFEs) and their polymerization products

Description

LUBRICATION IN METAL WORK FIELD OF THE INVENTION The present application is related to lubrication, especially it is related to various metal working processes, including non-cutting forming processes and cutting machining processes. Training processes include metal cable stretching, tube forming in seamless or welded modes, tube rolling, forging (including thickened, - stamping, and threading), rolling (including flat and rolled product), extrusion, sheet manufacturing process, including punching, coining, bas-relief drawing, embossing, shearing, forming, stamping, and forming by narrowing, metal cutting and machining operations, including cutting, drilling, widening, boring, capping, milling, brushing, hole broadening, sawing, internal threading, recessing, and turning, and abrasive cutting, grinding, bending, polishing, and bending. These various operations are performed on factory products and / or manufactured parts (work pieces). BACKGROUND OF THE INVENTION Many metal forming and cutting processes use lubricants to cool the work and the tool, removing the metal by flow in the cutting processes, decreasing the friction between the tool and the work piece, and as a barrier layer to prevent the binding or formation of cookies. The extension of these various lubrication needs differs between the various metal working processes and as well as with respect to a particular process as such applied to different metals. This is illustrated by the situations of lubrication requirements for stretching refractory metal cables (Ta, Nb, Mo, Ti, Zr, Hf and alloys) and steel and common ferrous metals and non-ferrous metals (Fe, Cu, Al, Ni, and alloys, such as INCONEL ™ and steels) and precious metals (Au, Pt, Pd, Rh, Re). The term "metal" as used herein includes those ceramics. as ceramic metals that are workable in much the same way as metals and where lubrication is employed to reduce tool wear and / or otherwise improve the metal working process. Because of the severe sliding contact between the workpiece and the tool, lubricants are used in all metal working operations to reduce friction between the workpiece and the tool, to rinse the tool and prevent the progressive accumulation of crusts and dirt on the surface of the tool, to reduce wear and filings between the workpiece and the tool, to remove the heat generated during the plastic deformation, and to protect the surface characteristics of the finished workpiece. The lubricants used today to work common metals are a complex mixture of different esters; soaps; solid lubricants, such as graphite, TEFLON ™, fused fluorides, MoS2, S2, MoSe2, and similar solid lubricants; and other extreme pressure lubricants. Oil-based lubricants or polyglycols are frequently used in the form of emulsions in water at concentrations of the order of 10%, sometimes with additives to give the emulsions the necessary detergency to keep both the workpiece and the tool clean. The ease of cleaning is a fundamental parameter in the selection of metal working lubricants. In the state of the art, these kinds of lubricants have been found to be inadequate, e.g. ex. , in the production of refractory metal cable. This is particularly important in solid lubricants. It is well known that stretched cables and tubes, particularly of refractory metals, present the most extreme conditions of metal work from the point of view of friction forces between the tool and the workpiece, the tool wear, and the stresses experienced. for the piece of work. Consequently, for purposes of illustration only, the following discussion will deal with the stretching of metal and refractory pipe and cable and, with the understanding that the discussion applies equally to other metal working operations and workpieces of another metallurgy. Various chlorinated oils have been used on phosphate precoats, as well as mixtures of various disulfide lubricants such as graphite and molybdenum with limited success in stretching the refractory wire of the metal. More recently, chlorotrifluoroethylene (CTFE) based oils have become the lubricant of choice in the production of refractory metal cable, generally in a viscosity range of 20 to 150 centistokes. While CTFE lubricants are now used almost exclusively in the production of tantalum cable in electronic grade, they present a number of serious active limitations. Because of the poor heat transfer characteristics of CTFE lubricants, the rates of stretching must be widely spaced, generally in the range of 100 to 300 FPM. The typical stretched speed cable for common metals is in the range of 5000 to 20,000 FPM. As a result, the stretching costs for refractory metals are very high by comparison. In addition, CTFE lubricants are only marginally effective in reducing and irritating wear between the cable and the die and in dragging the wear products away from the die entry. These problems are very evident in the short die life (<20 pounds per set) obtained when carbide is used in the die to stretch the tantalum and in continuous problems with surface roughness and dimensional control (including both diameter and roundness). All these limitations, associated with CTFE lubricants, make the stretch metal refractory cable and process inherently high cost with less desired product quality.

A more serious limitation of CTFE lubricants is found when testing to remove them from the surface of the finished cable. The removal of these lubricants is typically done using solvents, typically 1,1,1-trichloroethane. With the increasing restrictions placed on solvent use because of flammability, toxicology, ozone depletion, and global warming, it is almost completely impossible to remove CTFE lubricants from cable products. A number of hot, aqueous and degreasing systems, with and without ultrasonic, have been used to try to remove these lubricants with limited success, CTFE lubricant residues on electronic grade cable surfaces continue to be a cause of electronic component failure . The first step in the production of seamless metal tubes is often carried out by rolling or previously by round rolling of ingots. The produced heavy wall tube is removed as a tube shell. A number of different manufacturing methods are used, depending on the wall and diameter of the required tube thickness. The oldest method of making seamless pipes is the Mannesmann boring process, which uses the helical laminator principle. The machine comprises two steel rollers whose axes are inclined to each other. Both rotate in the same direction. The space between rollers converges to a minimum width called throat. Just beyond the throat is a drilling mandrel. A solid round metal bar, rotating in the opposite direction to the rollers, is inserted between the rollers. When the main end of the bar has advanced to the throat, it finds the mandrel, which thus forms a central cavity in the bar as it continues to move through the rollers. The tube produced with a thick wall by the Mannesmann process can be reduced to a thin wall tube by passing it through the special rollers in a so-called Pilger mill. These rollers vary in cross-sectional shape around their circumference. The tube, fixed to the mandrel, is first supported by the narrow portions of the rollers. The rotation of the special rolls, so that the progressively thicker portions of the rolls contact the tube and generate more and more compressive forces on the wall of the tube, reduces the thickness of the tube wall until each roll has rotated to such an extension of the one that part very large of its cross section is reached and the tube, in this way, no more sustained. The tube is then pulled a certain length so that again a thick walled portion of the tube is held by the rollers. The mandrel is rotated at the same time in order to ensure uniform application of the roll pressure around the entire circumference of the tube. A second common method of manufacturing seamless metal pipes is the Stiefel boring process, where a round bar is first drilled in a rotary milling machine and the heavy wall shell obtained in this way is then reduced in a second Horadación operation, in a frame of rollers of two heights, to form a thinner tube boarded. A third common method of manufacturing seamless metal tubes is the forging rotary process, wherein a square ingot, heated to the rolling mill temperature, is formed into a closed shell at its end. This shell is then reduced and stretched on a rotary hole mill and finally passed by four-roller assemblies, arranged on the circumference of the tube at intervals of 90 °, by means of which the diameter is progressively reduced. A fourth common method of manufacturing seamless metal tube shells is by extrusion, wherein a rod is forced between a die and mandrel (to maintain the central cavity of the tube). The extruded tube shells are then reduced to the final wall and diameter thickness by using one of the processes described above. Extrusion is a metal working process used to produce long products, straight metal including bars, tubes, hollow sections, rods, cables, and belts. In this process, an ingot, disposed within a close container under the high load, is forced by a die to produce an extrusion having the desired cross section. The extrusion can be carried out at room temperature or at elevated temperatures, depending on the metal or alloy to be processed.

The cold extrusion process is used extensively for the extrusion of low-liquefaction metals, including lead, tin, aluminum, brass, and copper. In this process, the ingots are placed in a chamber and are axially compressed. The metal flows through a die having one or more openings to form the cross section of the product to be extruded. The most widely used method to produce extruded forms is the process of direct hot extrusion. In this process, a heated solid metal or a metal may contain metal or ceramic powder or a preform or the like which is put in a chamber and then axially compressed by a screw jack. The opposite end of the cylinder the ram contains a die having a hole of the desired shape or a multiplicity of holes. Like direct, hot extrusion, the hydrostatic extrusion process involves the strength of a solid ingot metal or a metal that may contain ceramic powder metal or a preform through a conveniently formed orifice under compressive forces. In both processes, the workpiece or the like is placed in a chamber, one end of which contains a die having a hole of the desired shape or a multiplicity of holes found. As not direct, the hot extrusion process, where the compressive forces that operate on the work piece are generated by the direct contact between the work piece and a pile driver, the compressive forces in the hydrostatic extrusion process are translated into the piece of work indirectly by means of a pushing means (mass of powder or liquid) that surrounds the work piece. Hydrostatic extrusion has been applied to almost all materials, including aluminum, copper, steel, and ceramics. In addition, metal extrusion is also referred to as pitching, pressing, forging, extrusion forging, pressure extrusion, and impact extrusion. The cold-pitching process has become popular in both the steel and non-ferrous metals working fields. The original process consists of a punch (usually moving at high speed) hitting a target (or ingot) of the metal to be extruded, which has been put into the cavity of a die. The authorization is on the left between the punch and the die walls. As the punch comes into contact with the target, the metal has nowhere to go except through the annular opening between the punch and the die. The punch moves at a distance that is controlled by a placed grip. This distance determines the base thickness of the terminal part. The advantages of cold extrusion are the highest strength of the extrusion because of the severe hardening tension, a good conclusion, is the dimensional accuracy, and a minimum of processing required. However, the increased friction between the target and the die requires a highly efficient lubricant that ensures extrusion that conforms to the desired technical specifications and that the target does not get stuck in the die. Hollow tubes or cylinders that are manufactured by these aforementioned processes are frequently cold-terminated by stretching. Cold drawing is used to obtain closer dimensional tolerances, to produce the best surface results, to increase the mechanical properties of the tube material by the hardening tension, to produce tubes with thinner walls or the smaller diameters that can be obtained with hot forming methods, and to produce irregular shaped tubes. Tube stretching is similar to stretched cable. The tubes are produced on a row or the bull block and with dice similar to those used in the stretched cable. However, in order to reduce the wall thickness and precisely control the inside diameter, the inside surface of the tube must rest while passing through the die. This is commonly done to put a mandrel inside the tube. . The mandrel is frequently secured at the end of a stationary rod attached to the end of the row and positioned so that the mandrel is located in the hole of the die. The mandrel may have a cylindrical or a crossover cross section. The tubes can also be removed using a moving mandrel, or by pulling a long rod through the die with the tube or by pushing a deep shell contracted by the die with a punch. Because of difficulties in using long mandrel rods, the tube that is stretched with a rod is commonly limited to the production of the large diameter pipe. For small diameter tubes, the rod that supports the stationary mandrel will thin too much to have adequate strength. Another method for forming a tube is the collapsed tube, in which no mandrel is used to support the inside surface of the tube as it is removed by the die. Since the entrance of the tube is not supported by the sunk tube, the thickness of the wall will not increase or decrease in a manner dependent on the conditions imposed in the process. On a commercial basis, this type of tube production is used only to produce small tubes. However, the sunken tube represents a major problem in plastic forming theory because it occurs as the first step in the tube that is stretched with a mandrel. In order that the dimensions of the tube can be controlled by the dimensions of the mandrel, it is necessary that the inside diameter of the tube be reduced to a value slightly smaller than the diameter of the mandrel by a process of collapsing the tube during the early stages of its passage through the die The tubes have been produced from all common metals, including steel, copper, aluminum, gold, silver, etc., as well as from refractory metals, including tantalum, niobium, molybdenum, tungsten, titanium, zirconium, and their alloys and the like. Because of the severe sliding contact between the tube and the die, and between the tube and the mandrel, the lubricants are used in tube forming operations to reduce the friction between the tube and the formation of tools, to rinse the tools to prevent the Progressive accumulation of fines and dirt on the tool surface, to reduce wear and irritation between the tools and the pipe, to remove heat generated during plastic deformation, and to protect the surface characteristics of the finished pipe. As with the stretched cable, ease of cleaning is a fundamental parameter in the selection of laminated tube lubricants. Lubricants in the state of the art have been found to be inadequate in the production of metal refractory tubing. The poor heat transfer characteristics of CTFE lubricants greatly limits the drawing speeds, generally in the range of 50 to 100 FPM. The typical stretched velocity tube for common metals is in the range of 1,000 to 4,000 FPM. As a result, the stretching costs for refractory metals are very high by comparison. In addition, CTFE lubricants are unique to the effective margin in reducing and irritating wear between the tube and the die and in sprouting the wear products away form the die entry. These problems can lead to a short life of the die with surface roughness and dimensional control (including both diameter and roundness). Also, as in the stretched cable, CTFE lubricants can leave difficult residues (on the outer and inner surfaces of the finished tube). An additional problem occurs with tubes that can not be cooled. These are drawn in direct lengths on stretch benches, which use speeds generally up to 1000 FPM. Therefore, the tendency to form a partially hydrodynamic film is greatly reduced, even outside. the surface of the tube. The conditions are even more severe to the internal surface; good coverage can not be guaranteed by drawing pastes or solid soaps, even when applied by dipping, and lubricant failure will often lead to irritating dry spots. Liquid lubricants can be applied more easily to the inner surface of the tube, but few liquids are efficient lubricants with sufficient cohesion to prevent any metal-to-metal contact, and those that frequently promote corrosive wear of the mandrel (eg. chlorinated oils). These problems are duplicated in any case, since the wear is evident on the plugs as well as on dice. These difficulties are greatly magnified when less reactive materials, such as titanium alloys or stainless steels, are going to be stretched.

It is an object of this invention to provide improved metalworking processes using a lubricant that provides superior lubrication against conventional lubricants. Another object is to improve the working metals process in a way avoiding previous problems. A further object of the invention is to use a conventional metal process worked a non-flammable and non-toxic lubricant. It is another object of the invention to use a lubricant having a zero ozone depletion potential (ODP) in a conventional metalworking process. It is still another object of the invention to use in a conventional metalworking process a lubricant that is photochemically unreactive in the atmosphere, is not a precursor of photochemical smog, and is free of volatile organic compounds (VOC) according to the definitions of various countries and international organizations. Similarly, it is an object of this invention to provide an improved lubricity process by providing and avoiding the above problems. It is a further object of the invention to reduce wear of metals and associated components in process that involve lubrication, but are not generally considered as the metal working process, e.g. ex. , the engagement operation, chain management, and transmissions on lubricated covers or in open mode; and the axes that move alternately or axially on presences, newspapers, or metal linings. BRIEF DESCRIPTION OF THE INVENTION The present invention, as applied to processes and equipment (machines) for stretching the cable, for stretching, plunging, or rolling mill tubes, strip milling, shortening, coining, forming seamless metal tubes, forging, and extrusion, preferably using fully and highly fluorinated lubricants and particularly are preferably applied to make fabricated refractory metal products and fabricated parts. Preferred machines and processes employ a lubricant comprising one or more of: (a) perfluorocarbonated compounds (PFCs), including aliphatic perfluoroalkanes (a-PFCs) having the general formula CnF2n + 2, (b) perfluoromorpholinos (PFMs) having the general formula CnF2n +? ON, (c) perfluoroamines (PFAs), (d) highly fluorinated amines (HFAs), and their respective polymerization products. Such totally and highly fluorinated carbon compounds are exposed to a very high degree of thermal and chemical stability due to the strength of the fluorine carbon bond. The PFCs are also characterized by extremely low surface tension, low viscosity, and high liquid density. These are clear, colorless and odorless liquids with boiling points at approximately 30 ° C to approximately 300 ° C. These liquids may be used alone or in combination with inert fillers, such as in fats, pastes, waxes, polishes, and the like. The fluorinated and inert liquids are used according to the present invention which can be one or mixed of a-PFC, PFM, PFA, and HFA of compounds having from 5 to 18 carbon atoms or more, optionally containing one or more heteroatoms chain, such as divalent oxygen, hexavalent sulfide, or trivalent nitrogen and having a radius of H: F low 1: 1, preferably have a hydrogen content of less than 5% by weight, most preferably less than 1% by weight . These materials can be used only in the liquid phase, mixed or emulsified with other functional or transport liquids and / or mixed with solid particles such as pastes (eg, mixed with known particle forms solid lubricants such as neodymium fluoride, sulphate molybdenum, tungsten sulfate, molybdenum selenide, molybdenum telluride, graphite, TEFLOW ™, fused fluorides and similar solid lubricants). The carrier agents for the fluorinated liquids according to the process of the invention can be provided, e.g. ex. , greases, pastes, waxes and polishes. Suitable inert fluorinated fluids useful in this invention may particularly include, for example, perfluoroalkanos, such as perfluoropentane, perfluorohexane, perfluoroheptane, and perfluorooctane.; perluoroamines, such as perfluorotributylamino, perfluorotriethylamino, perfluorotriisopropylamino, perfluorotyrazilamino; perfluoromorpholino, such as perfluoro-N-methylmorpholino, perfluoro-N-ethylmorpholino, and perfluoro-N-isopropylmorpholino; and the polymerization products of these classes. The prefix "perfluoro" as used herein means that all, or essentially all, hydrogen atoms are replaced by fluorine atoms. Perfluorocarbon liquids were originally developed for use as heat transfer liquids. These are currently used in heat transfer, the steam welding phase, and electronic test applications and as solvents and cleaning agents. The term "highly fluorinated" used herein means having an H: F ratio below 1: 1. Commercially available inert fluorinated fluids useful in this invention include FC-40, FC-72, FC-75, FC-5311, FC-5312 (available from the 3M Company under the trade name of "Fluorinerte", The Product Bulletin 3M 98-02110534707 (101.5) NP1 (1990)); LS-190, LS -213, LS-260 (available from Montefluos S.A., Italy); and Hostinert-175, 216, 272 (available from Hoechst-Celanese). Important, because PFCs are highly or totally fluorinated, and therefore do not contain chlorine or bromine, and have zero ozone depletion potential (ODP). the above liquids are also non-flammable and non-toxic, because they are photochemically non-reactive in the atmosphere, are not precursors to photochemical smog and are exempt from the definition of the Federal Volatile Organic Compound (VOC). In addition, PFC liquids cost significantly less than chlorotrifluoroethylene oils currently in use. Accordingly, these inert fluorinated fluids are advantageous for the processes described herein and PFCS are then the preferred lubricants in good drawn wires at high speeds of refractory metals. In the process of stretched cable, perfluorocarbon liquids have greatly extended the ranges of the stretched cable important variable and available to the manufacturing process. While using CTFE lubricants, die reduction is limited to approximately 15%. The use of PFC lubricants allows reductions as large as 26% per die. This will allow the next generation of cable pulling equipment to be much more productive. In addition, when operating the speeds can be increased by more than ten times, further reducing the number of machines to stretch the cable required a certain level of production. CTFE lubricants were limited to approximately 200 FPM while the PFC lubricants have been used at speeds of over 2,000 FPM with no sign of having reached an upper limit. In addition, die wear is minimized to the point that the cable can be stretched without quenching from 0.103"(2.5 mm) to the final diameter of 0.005" (0.127 mm) with a die life of more than 200 lbs. Of finished cable. contracted hard.

In the process of the stretched tube, the perfluorocarbon liquids greatly extended the ranges of the important variable stretches available to the manufacturing process. While conventional lubricants are used, the reduction per pass is limited to about 10-15%. The use of PFC lubricants allows reductions as large as 30%. This allows new and modified processes and equipment for tube stretching that are much more productive. The speeds of operation can be increased by more than ten times, greatly improving the passage of a certain production facility. Conventional lubricants are limited to approximately 100 FPM while PFC lubricants can be used at speeds of over 2,000 FPM. The PFC lubricants of the current invention improve the production of smaller tubes of diameter, particularly hypodermic needles and capillary tubing 0.005 to 0.125"(.127 to 3.17 mm) in diameter having a wall thickness in the range of 0.001" to 0.050. "(.025 to 1.27 mm) The tantalum cable and the stretched tube are created in the field of metalworking under the most severe active conditions that require lubrication.The results shown even establish feasibility for a metalworking process less severe and with the other, more ductile and malleable materials All grades of perfluorocarbon liquids evaluated to date have been used to produce high quality tantalum cable and tubes PFC fluids run from the 3M PF-5050 (C5F? 2) having a boiling point of 30 ° C and a viscosity of 0.4 centistokes to perfluoroamines having the general formula CnF2n + 3N, such as FC-70 of 3M (a mixture of perfluorotripropylamino ( C3F9N) and perfluorotributylamino (C FnN) a boiling point of 215 ° C and a viscosity of 14 centistokes, to another PFCS (p. ex. , perfluorotributylamino, perfluorotylamilamino, and perfluorotripropylamino) having boiling points up to 240 ° C and a viscosity of 40 centistokes at room temperature all have been used to produce high quality cable at high stretch speeds and high quality of high rolling mill tubes and / or speeds of stretching. The FC-40 of the 3M Company (perfluorotripropylamino (C3F9N)) has been extensively evaluated because of its combination of low price and high boiling point (155 ° C). This liquid has a viscosity of only 2 centistokes and vapor pressure at room temperature of 3 torr. All the data suggest that there are many other PFC fluids that are good »lubricant of metal work. The fact that the lubrication characteristics are not dependent on the viscosity of liquid PFC is unique to this class of liquids and is not understood even from the point of view of the current theory of lubrication of metal work. In fact, the use of a working metal lubricant has a viscosity of less than 1 centistoke is contrary to most lubrication theories.

In addition, a greater reduction in the amount of thin submicron tantalum residue scale produced during the aforementioned stretching processes has been observed. While conventional lubricants are used, the lubricant becomes black and "tarry" due to high concentrations of tantalum fines in a few hours. When PFC liquids are used, liquids can be kept in clear glass using a simple filter. In contrast to conventional lubricants, PFCs vaporize off the surface of the tube as it exits the machine. Thus, not only does the use of these lubricants result in a smoothing, cleaning, and better performance of the product than is possible with conventional lubricants, but a subsequent cleaning step is not required, as with conventional lubricants. A variety of metalworking tasks can be improved by the process already mentioned. The particular benefits are realized in the context of making fine tantalum cable to be used as main anode cables in tantalum electrolytic capacitors. The tantalum cable (typically 5 mils to 20 mils (0.127 mm to 0.508 mm) in diameter) is bonded to an anode of porous, embedded powder, or is embedded here in advance prior to embedding and also secured in the inlay. Minimizing the loss of the capacitor using such an anode depends in part on the cleaning of the main cable, which is directly affected by the selection of lubricant. The significant reduction in DC cable shrinkage has been achieved with cables produced according to the current invention. The current shrinkage is directly related to the surface topography of the cable, as well as the amount of lubricant that is trapped in the cracks and openings on the surface of the cable. The present decrease in DC can be reduced by producing a smoothing agent for the cable surface and removing the residues of the lubricant from the surface of the cable. The DC shrinkage is measured by anodizing a cable length to complete the surface covering with a dielectric tantalum oxide film. This anodized wire is put into an electrolyte and a DC voltage is applied to the tantalum lead by itself. The DC current "spillage" by the dielectric film is measured at a fixed voltage. This derating current is a measure of the integrity of the dielectric film. The integrity of the dielectric film itself is a measure of the total cleanliness and roughness of the cable surface. Producing a smooth surface free of residual lubricants, the improved dielectric films are produced, thus improving the characteristics of DC loss of the cable and the anode that has the cable attached to it. In sum, the important benefits are given within a framework of tantalum tubes made to be used as tubes in heat exchangers. The tantalum tube (typically 10 to 40 mm in diameter) is used in heat exchange applications in the chemical process industry where no other metallic material will survive. The benefits are also realizable under another, less severe operating conditions, including another process of metal work and with another, more ductile and malleable materials (that is, the metals, defined here, that present a work task of metals of severity similar or greater). The present invention is also applicable to general lubrication applications, such as the case of lubrication, presence lubrication, and the like. The invention is generally not applicable to elevated metal temperature working processes at temperatures above the temperature decomposition of fluorinated liquids (>600 ° C). The temperatures to be considered are the result of external heating applied to metal working machines or cut surfaces and / or the work piece (eg, an ingot heated prior to extrusion) and by the mechanical contact between the tool surface and the work piece. Boiling may occur at the end of the lubricated metal working process and frequently occurs in cold and hot processes (and even in normal hot processes) that are improved by the current invention. The vapors form the fluorinated liquid can be coated by condensation with the use of cooled surfaces. The condensed liquid can be reused without reconditioning.

The invention also includes the use of compression powder metallurgy in which the inert fluorinated materials in the liquid or solid form are useful as the coatings of metal particles, e.g. ex. powder and / or desquamate primary or secondary (pre-agglomerated) when the particles are to be pressed in a mold or isostatically. The particles may fall with the liquid in a mixer until completely coated, in a manner similar to the normal coating with the normal / bound lubricant such as stearic acid. The initial pressure produces a. compact coherent commonly of a porous shape with point to point between welded particles. Then the compact heats up the boiling point of the fluorinated cover by handling it out through the porous mass leaving essentially no residue of the fluorinated compound. Depending on the application of the end use, the agreement can be used as such or additional consolidated and strengthened by pressure and / or hearing in cold pressure, hot pressure, embedding or other known steps of the process. The fluorinated inert liquid can be used alone or with co-lubricants in the firm metallurgical powder. Its use can be limited to covering the metal particles or (in combination with suitable solid materials including co-lubricants) forming a matrix within the agreement and / or compromising the compact together before pressing. In such cases the matrix as a whole including the fluorinated inert material is removed by means of conventional de-packing techniques after the initial firmness of the metal. Boiling away from the inert fluorinated material and co-lubricant (s) is preferred. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the electron micrograph review at 300X and 1000X of the stretched cable surface using FC-40 perfluorocarbon liquid at 200 ft / min (61 m / min). FIG. 2 shows the electron micrograph review at 300X and 1000X of the drawn cable surface using PFC FC-40 liquid at 500 ft '/ min (152.4 m / min). FIG. 3 shows the electron micrograph review at 300X and 1000X of the drawn cable surface using PFC FC-40 liquid at 1,000 ft / min (304.8 m / min). FIG. 4 shows the scanning of electron micrographs at 1000X from the surface of two stretched cable samples using a CTFE lubricant at 200 ft / min (61 m / min). FIG. 5 shows a 2500X SPM micrograph of a 50μ2 area of the stretched cable TPX surface with CTFE lubricant. FIG. 6 shows a 2500X SPM micrograph of a 50μ2 area of the stretched cable TPX surface with PFC FC-40 liquid. FIG. 7 shows a 2500X SPM micrograph of a 50μ2 area of the tantalum cable surface stretched condenser grade with CTFE lubricant.

FIG. 8 shows the reference of the micro-FTIR spectrum of the PFC FC-40 3M liquid. FIG. 9 shows the micro-FTIR spectrum of the extract of a sample of the tantalum capacitor grade cable together with the reference spectrum of the PFC FC-40 liquid. FIG. 10 shows the micro-FTIR spectrum of the extract removed from a sample of the tantalum capacitor grade cable after cleaning in an ultrasonic strand cleaning system used for the tantalum cable stretched capacitor grade on a production basis. FIG. 11 shows the as clean micro-FTIR spectrum sub-imposed on the reference spectra of a CTFE oil and an ester rod-based laminator oil. FIG. 12 shows how - received shrinkage in μA / cm2 of TPX cable as drawn with PFC FC-40 liquid. FIG. 13 shows a schematic of a rescued PFC liquid and recirculating apparatus for use in the drawn cable. FIGS. 14 A-D shows the review of 300X and 4500X electron microscope images of the stretched copper ETP cable with FC-40 and a stretched hydrocarbon based copper lubricant. FIGS. 15 A-B show the review of electron microscope images of stretched tantalum tubes with FC-40 and CTFE lubricants.

FIGS. 16 A-B show the review of probe microscope images of the surfaces of the stretched tantalum tubes with FC-40 and CTFE lubricants. FIG. 17 shows a scanning electron microscope image of the stainless steel wire surface .0993"302 with perfluorocarbon liquid L13557. FIGS 18 AC show the 4mm surfaces of the tantalum nuts made using perfluorocarbon liquid L13557. DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The practice of the invention according to preferred embodiments thereof is indicated by the following non-limiting examples: Example 1: 169.5 lbs (77.1kg) of 0.0098"(0.0249 cm) of tantalum cable halved Stretched using a Heinrich cable stretching machine (MODEL # 21W21) using FC-40 perfluorocarbon liquid (Compañia3M) as the lubricant. The cable speed ranged from 200 ft / min (61 m / min) to 1386 ft / min (424.5 m / min). The average roundness was measured using a laser micrometer at the beginning of each of the cable coils that was 16 millionths of an inch (40.6 μm) with the average roundness at the end of each spiral averaging 18 millionths of an inch (45.7 μm). An average of 42.4 lbs of the cable was produced by the set of dies.

Example 2: 70.2 lbs (31.9 kg) of 0.0079"(0.0201 cm) extra-hard tantalum disposition wire was stretched by a Heinrich wire stretching machine, as in Example 1, using FC-40 perfluorocarbide liquid 3M as the lubricant.The cable speed ranged from 500 ft / min (152.4 m / min) at 1000 ft / min (304.8 m / min). The average roundness at the beginning of each of the cable spirals was 11 millionths of an inch (27.9 μm) with the average roundness at the end of each spiral with an average of 11 millionths of an inch (27.3 μm). An average of 35.1 lbs of cable was produced by the set of dies. Example 3: 231.8 lbs. (105.4 kg) of 0.0079"(0.0201 cm) of hard tantalum disposition cable was stretched by a Heinrich cable stretching machine, as in Example 1, using the 3M FC-40 perfluorocarbon liquid as the lubricant. cable ranged from 800 ft / min (243.8 m / min) to 1480 ft / min (451.1 m / min). The average roundness at the beginning of each of the wire coils was 12 millionths of an inch (30.5 μm) with the average roundness at the end of each roll averaging 16 millionths of an inch (40.6 μm).

An average of 46.4 lbs of cable was produced by the set of dies. Example 4: 49.4 lbs (22.5 kg) of 0.0075"(0.0191 cm) hard laying tantalum cable was stretched by a Heinrich wire stretching machine, as in Example 1, using the 3M FC-40 perfluorocarbide liquid as The cable speed ranged from 1480 ft / min (451.1 m / min) to 1600 ft / min (487.7 m / min) The average roundness at the beginning of each of the cable coils was 15 millionths of an inch ( 38.1 μm) with the average roundness at the end of each spiral that averages 17 millionths of an inch (43.2 μm) An average of 24.7 lbs of cable was produced by the set of dies Example 5: 71.6 lbs (32.6 kg) of 0.091"(0.0231 cm) of tempered tantalum disposition wire was stretched by a Heinrich wire stretching machine, as in Example 1, using the 3M FC-40 perfluorocarbon liquid as the lubricant. The cable speed was 1200 ft / min (365.8 m / min). The average roundness at the beginning and end of each of the wire coils was 20 millionths of an inch (50.8 μm). An average of 71.6 lbs of cable was produced by the set of dies.

Example 6: In addition to the evaluation of property performed mechanically, dimensionally and visually normal, on the cable as it is produced, the stretched cable used perfluorocarbon lubricants were evaluated using an electron microscopy review (SEM). Electron micrograph scanning took 300X and 1000X of tantalum cable stretched capacitor grade using FC-40 at 200 ft / min (61 m / min), 500 ft / min (152.4 m / min), and 1000 ft / min (304.8 m / min) shown in FIGS. 1-3 respectively. The 300X frames show that the quality of the cable surface actually improves with the increasing speed of stretching. Total, the frequency and the depths of the cracks and openings on the surface of the stretched cable using liquid perfluorocarbon lubricant decreases with increasing the speed of the stretched cable.

Example 7: The surface of a stretched grade tantalum capacitor cable using a CTFE lubricant at 200 ft / min (61 m / min) is shown in FIG. 4 to 1000X. This chart shows the typical structure seen on the stretched cable using a conventional chlorotrifluoroethylene lubricant. As can be seen, this cable shows a great deal of damage to the surface, particularly in a relatively thin platelet form of the material torn from the surface of the cable. This appears to be the mechanism by which most of the "fines" observed in the good process of the stretched cable are generated. The fact that fines are not observed in the drawn cable using the perfluorocarbon liquid lubricant indicates that the surface damage is due to this peeling caused by irritant and ignited (as a result of decomposed lubricant) has been eliminated. Example 8: In order to evaluate the total degree of cleanliness of the contracted wire produced using a perfluorocarbon lubricant, the samples were subjected to micro-FTIR infrared analysis. The reference spectrum of the 3M FC-40 lubricant is shown in FIG. 8. The chlorine methylene extract spectrum from a TPX 401G sampling of the drawn cable using the perfluorocarbon lubricant, together with the reference spectrum of the FC-40, are shown in FIG. 9. It is important to note that essentially no lubricant residue of any kind is on the cable, and that any residue that is present is definitely not FC-40. The total absorbance values can be compared to the data shown in FIG. 10, which shows the FTIR spectrum of the extract removed from a TPX 501G sample after cleaning in an ultrasonic strand cleaning system used to remove CTFE lubricants. The values of total absorbance on the order of 0.1 absorbance units are typical of the clean cable in the unit. In general, these absorbance values represent less than one monostratum of residual lubricant on the surface of the cable. The perfluorocarbon cable as stretched has less than 20% of this amount of surface contamination and is truly an electronically clean material. FIG. 11 shows the already clean sub-tax spectrum on the CTFE oil reference spectra and an oil-based rod-laminator ester used in earlier stages of the cable production process. These two materials account for essentially 100% of the residue found on the surface of our dirty cable condenser grade. There is no indication of any residual FC-40 found. As a result of this analysis, it appears that the stretched cable using the perfluorocarbon lubricant can be used as a stretch. The subsequent ultrasonic cleaning will only serve to contaminate the surface of the cable. Example 9: In order to further investigate this finding experimentally, the samples of both 0.0079") 0.0201 cm) and 0.0098" (0.0249 cm) of the diameter of the cable were subjected to as received shrinkage tests. The DC shrinkage is measured by anodizing a cable length to completely cover the surface with a dielectric tantalum oxide film. This anodized wire is put into an electrolyte and a DC voltage is applied to tantalum lead to itself. The DC current "spillage" by the dielectric film is measured at a fixed voltage. This derating current is a measure of the integrity of the dielectric film. The integrity of the dielectric film itself is a measure of the total cleanliness and roughness of the surface of the cable surface. By producing a smooth surface free of residual lubricants, the improved dielectric films are produced; to improve DC cable shrinkage characteristics. These data are shown in FIG. 12 and indicate that the values of shrinkage received by contracted cable falls in the range of 1 to 3 μamps / cm3. They certainly compare favorably with recent production and compare very favorably with the maximum specification of 10 μamps / cm3 usually seen in the industry. Example 10: To evaluate the effectiveness of perfluorocarbon liquids for use in copper cable drawing operations, the copper cable's .0120 diameter ETP was produced using an instrumented laboratory with a cable stretching machine using FC-40 and an oil based hydrocarbon for stretching copper having a viscosity of about 20 centistokes as the stretch lubricants. Stretching force was measured when the cable was stretched to .0128"in diameter by the last die to produce .0120" of cable diameter, a reduction of 12.1%. The force observed when using FC-40 was 560 grams compared to the observed force of 720 grams when a hydrocarbon based on a lubricant was used to stretch copper.

The scanning of electron micrographs, taken at 285X and 4500X magnifications, of the stretched copper ETP cable using both lubricants are shown in FIG. 14. While the cable surfaces stretched with both lubricants are similar to the low amplification, the high magnification test reveals many chevron cracks formed on the stretched hydrocarbon lubricant sample indicating grain boundary separation which may result in cable fracture if the extra stretch was to be tested. Example 11: The surface of the stretched tantalum tubes using both F-40 and CTFE lubricants was examined using the scanning electron microscope. FIG. 15A shows the surface of a diameter of. 250"of the tube having a .010" wall thickness stretched using FC-40 at a magnification of 315X. FIG. 15B shows the .500"diameter surface of the drawn tube using a CTFE oil at a magnification of 319. These micrographs clearly show the extensive loss of metal from the surface of the drawn tube using the CTFE oil. Surface roughness between these tubes, the samples of both were examined using a scanning probe microscope.Fig.16A shows the three dimensional images of the surface of the drawn tube using FC-40 having an average surface roughness (Ra) of 93.15 nm FIG. 16B shows the three dimensional images of the surface of the drawn tube using a CTFE oil having an average surface roughness of 294.92 nm. These data show that the tube drawn using the CTFE oil had a surface roughness value three times more than the drawn tube using FC-40, a perfluorocarbon liquid. Example 12: To evaluate the effectiveness of perfluorocarbon liquids for the use of stainless steel wire drawing operations, 0.139"diameter 302 stainless steel wire was obtained from the Carpenter Technology and stretched by four consecutive reductions using liquid of perfluorocarbon L13557 as a lubricant to the 0.0993"diameter cable product. Using normal practices to stretch stainless steel, three unique reductions at 18% are possible without tempering the cable and coated with a phosphate lubricant conveyor. An SEM image of the .0993"surface of the stretched cable using the perfluorocarbon lubricant is shown in FIGS. 17 to 255. This image clearly shows the presence of the phosphate lubricant carrier on most of the surface of the cable after four reductions to 18% Example 13: To evaluate perfluorocarbon liquids in tantalum processing operations, an experimental perfluoroamine liquid was replaced by the CTFE oil normally used in sequential processing operations to produce 4mm of tantalum nuts. They produced from pricked targets in a series of processing operations including drilling, exploitation, rollover and fronting operations.The introduction of L13557 resulted in more than four increased folds in speed processing from 200 feet of surface per minute to> 850 feet of surface per minute while tool life increases by at least one factor of 10. When CTFE oils are used, the nominal pinch of the tool is resharpened every 50 to 100 pieces. Thus using L13557, the regrind tool occurs at intervals of more than 2000 pieces. Similar increases in tool life were observed for drills and taps as well. An image SEM at 25X. of a section of one of the 4mm of the nuts is shown in FIG. 18. This image shows the high quality of the finished surface obtained on the end of the thread of the surface as well as the nominal surface. The average terminal area (Ra) was consistently measured at better than 32 micro-inches . An SEM image of the wires at 31X is shown in FIG. 18B showing the optimal form of yarn obtained and showing no evidence of tearing. An SEM image split at 25X and 250X from the surface of one of the 4mm tantalum nuts made using L13557 is shown in FIG. 18C showing the total form of freedom tears and grooves typically found on elaborate tantalum surfaces. -r End of Numbered Examples - In real production assays that use FC-40 perfluorocarbide liquid from Company 3M, the most important advantages observed include a larger five-fold increase in die life, a ten-fold increase in the stretched cable, "electronically clean" as a contracted cable, and a fivefold reduction in the cost of lubricant. .r the pound of the stretched cable. In addition, a greater reduction by the sum of the submicron of the fine tantalum particle of the produced rubble has been observed. While using CTFE lubricants, the filters of the cable stretching machines are changed at the end of each production change. When PFC fluids are used, these filters change each one in two months. And, as shown in FIG. 13, the used PFC liquids can be rescued from the machine to stretch cable and recirculated, thereby reducing operating expenses and even further improving the environmental benefits that are possible. When the tubes are drawn from any metallurgy, the theoretical maximum reduction per pass (on a fixed cylindrical mandrel) is calculated as -1 / B '(1) qmax = 1 - 1 + 0.133B 1 + B where B' = 2_F as well where f is the coefficient of friction between the die and the workpiece for a particular lubricant, the apex angle of the die is now held at one half, in this case constant at 12 °. For normal lubricants, f normally varies between 0.05 and 0.15. For PFC liquid lubricants, f has been estimated at 0.003 to 0.005. Thus, B 'co nven t i ona l = (0. 1 0) = 1. 9 0 3 tan a and B 'pFc - 2 (0.005) = 0-095 tan a Therefore, qmax (conventional) = 35% and qma? (PFC) = 56%, sixty percent increases in the theoretical maximum reduction by the possible pass when using a PFC lubricant, compared to a conventional lubricant. It will now be apparent to those skilled in the art that other embodiments, improvements, details, and uses can be made uniform with the letter and spirit of the earlier discovery and within the scope of this patent, which is limited only by the following claims, interpreted according to the patent law, including the doctrine of equivalents.

Claims (24)

1. Claims: 1. The process for working metals comprising the lubrication of the metal during the working process with an inert fluorinated liquid selected from the group consisting of aliphatic perfluoroalkan having the general formula CnF2n + 2; perfluoromorpholino having the general formula CnF2n +? ON, wherein n is at least 5, and a boiling point of at least 50 ° C; perfluoroamines, having the general formula CnF2n + 3N, wherein n is at least 3, and a boiling point of at least 155 ° C; highly fluorinated amines; and its polymerization products; wherein said inert fluorinated fluids, occur in effective forms replaced and not replaced to allow the metal working process to be performed at high speed, but in a way that the lubricant residue requires its removal at the end of the process.
2. 2. The process according to claim 1 wherein said inert fluorinated liquid is provided in combination with at least one inert carrier agent, such as compositions selected from the group consisting of fats, pastes, waxes, and polishes.
3. 3. The process according to claim 1, wherein the material to be worked is a refractory metal.
4. 4. The process according to claim 3 wherein the refractory metal is tantalum.
5. 5. The process according to any of claims 1-4 wherein the metal working process is a stretched cable process with multiple die steps and the lubricant is the perfluorocarbon liquid and the cable when stretched has an average diameter between 5 and 10. mils (0.127 mm) and 20 mils (508 mm).
6. 6. The process according to claim 1 wherein, the fluorinated inert liquid compounds comprise the fluoroaliphatic compounds having 5 to 18 carbon atoms.
7. 7. The process according to claim 1 wherein the fluorinated, the inert liquid compounds comprise at least one chain heteroatom, selected from the group consisting of divalent oxygen, hexavalent sulfide, or trivalent nitrogen and has an H: F ratio below 1. :1.
8. 8. The process according to claim 6 wherein the fluorinated inert liquid compounds have a hydrogen content of less than 5% by weight.
9. 9. The process according to claim 7 wherein the fluorinated inert liquid compounds have a hydrogen content of less than 1% by weight.
10. 10. The process according to claim 1 wherein the perfluorocarbon liquid is selected from the group consisting of perfluoroalkanes.
11. The process according to claim 10 wherein the liquid is a perfluoroalkan the form selected from the group consisting of perfluoropentane, perfluorohexane, perfluoroheptane, and perfluorooctane.
12. 12. The process according to claim 1 wherein the perfluorocarbon liquid is a perfluoroamino.
13. 13. The process according to claim 12 wherein the perfluoroamino is selected from the group consisting of perfluorotributilaminos, perfluorotriethilaminos, perfluorotriisopropilaminos, and perfluorotriamilaminos.
14. 14. The process according to claim 1 wherein the perfluorocarbon liquid is a perfluoromorpholino.
15. 15. The process according to claim 14 wherein the perfluoromorpholino is selected from the group consisting of perfluoro-N-methylmorpholinos, perfluoro-N-ethylmorpholinos, and perfluoro-N-isopropylmorpholino
16. 16. The process according to claims 1-4 wherein the Metal is stretched to a thin form of the cable and secured as a main cable to a porous electrode mass.
17. 17. An anode of tantalum electrolytic capacitor and the attached main cable as made by the process of claim 20.
18. 18. The process according to any of claims 1-4 wherein the metal working process is the seamless mill, the metal tubes, comprising the steps of pulling a rod or large diameter tube in a machine for rolling the tube having at least one set of reduction rollers; lubricating the material during the rolling process with a liquid selected from the group consisting of perfluoroalkan having the general formula CnF2n + 2; laminating the tube or rod by at least one set of the reduction rollers lubricated with a perfluorocarbon liquid; and repeating the process until the necessary tube size is obtained.
19. 19. The process according to claim 18 wherein the tube has an average diameter between 10 mm and 50 mm and wall thickness between 0.5 mm and 10 mm.
20. The process according to any of claims 1-4 wherein the metalworking process is the drawing of the seamless metal tubes using multi-pass die and the lubricant is perfluorocarbon liquid and the drawn tubes have an average diameter between 0.005"(0.127 mm) and 2.0" (50.8 mm) and wall thickness between 0.001"and 0.050" (.025 to 1.27 mm)
21. 21. A lubrication process provided where the lubricant is a fluorinatadp, the inert liquid selec cited from the group consisting of aliphatic perfluoroalkan having the general formula CnF2n + 2, perfluoromorpholinos having the general formula CnF2n +? ON, perfluoroamines, and highly fluorinated amines; wherein said highly fiuorinated amine perfluoroamines and amines occur in substitute and not replaced forms.
22. 22. The process according to claim 21 wherein said fluorinated, the inert liquid is provided in which combination with at least one inert carrier agent, such as in compositions select from the group consisting of untos, pastes, encera, and lustres
23. 23. The process according to any of claims 1-4, 21 or 22 wherein the fluorinated inert liquid is mixed with a solid lubricant and provided in the solid form therewith as a paste, gel or other solid form. The process according to claim 23 wherein the solid lubricant is selected from the class consisting of graphite TEFLON ™, fused fluorides, MoS2, Ws2, MoS32, MoTe2 and similar solid lubricants. 29. The process according to any of claims 1-4, 25 or 26 wherein the metal working process is a firm powder metallurgy of the metal particles coated with said inert liquid. 30. The process according to any one of claims 27 or 28 wherein the metal working process is a firm powder metallurgy of the metal particles coated with said inert liquid and co-lubricant.