EP1019209B1 - An improved continuous casting mold system and related processes - Google Patents

An improved continuous casting mold system and related processes Download PDF

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Publication number
EP1019209B1
EP1019209B1 EP99938971A EP99938971A EP1019209B1 EP 1019209 B1 EP1019209 B1 EP 1019209B1 EP 99938971 A EP99938971 A EP 99938971A EP 99938971 A EP99938971 A EP 99938971A EP 1019209 B1 EP1019209 B1 EP 1019209B1
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Prior art keywords
mold
continuous casting
diamond
substrate
casting process
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EP99938971A
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German (de)
English (en)
French (fr)
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EP1019209A1 (en
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James B. Sears
John L. Knoble
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SMS Siemag AG
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SMS Demag AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/16—Controlling or regulating processes or operations
    • B22D11/20—Controlling or regulating processes or operations for removing cast stock
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
    • B22D11/059—Mould materials or platings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/16—Controlling or regulating processes or operations
    • B22D11/18—Controlling or regulating processes or operations for pouring

Definitions

  • This invention relates to the technical field of metal making and processing using the continuous casting process. More specifically, this invention pertains to an improved mold surface for a continuous casting machine, and to a system and method for controlling the casting process by actually monitoring the temperature of the casting at the mold surface while the machine is operating.
  • continuous casting machines typically include a mold that has two essentially parallel and opposed wide walls, and two essentially parallel opposed narrow walls that cooperate with the wide walls to define a casting passage of rectangular cross section. Molten metal is supplied continuously into a top end of the casting passage, and the mold is designed to cool the metal so that an outer skin forms before the so-formed slab or strand exits a bottom of the casting passage.
  • the mold casting surfaces are typically lined with copper or have a copper alloy surface layer and contain numerous passages through which water flows, during the molding process for rapid heat exchange.
  • the mold is cooled by spraying water directly against the cooler side of the mold liner.
  • the strand is further cooled by spraying as it travels away from the mold, until it becomes completely solidified. It may then be processed further into an intermediate or finished metal product, such as steel plate, sheeting or coils by traditional techniques such as rolling.
  • the mold casting surfaces also known as the "hot faces" of the mold, are exposed to the high temperature molten steel and corrosive mold flux for prolonged periods of time.
  • Copper is a very efficient thermal conductor, but is relatively soft and is thus susceptible to early wear and other types of degradation. Under normal casting conditions, the hot faces of the mold experience relatively rapid degradation such as wear, cracking and steam and chemical erosion. This effect is exacerbated in high-speed molds, which tend to run at higher temperatures wherein the copper material begins to further soften.
  • A.G. Industries, Inc. is the largest North American provider of maintenance and repair services for continuous casting machines, and is intimately familiar with the degradation and wear that occurs on mold faces during casting.
  • U.S. Patent 5,499,672 discloses a process for protecting a copper mold surface by applying a metal carbide protective material onto the mold surface.
  • Another protective coating technique involves applying a Ni-Cr alloy to the copper mold faces by a thermal spraying process. This process is described in the publication Ni-Cr Alloy Thermal Spraying of the Narrow Face of Continuous Casting Mold, dated May 1989 by Nippon Steel Corporation and Mishima Kosan Co., Ltd.
  • the strand or slab has a very thin skin when it initially forms in the mold. Rupture of the skin must be avoided at all costs because it can cause a condition known as a breakout, i.e., where molten metal escapes through the skin beneath the mold. A severe breakout can encase portions of the machine that are in its path in molten metal, rendering those components unusable and requiring them to be replaced and reconditioned.
  • a breakout i.e., where molten metal escapes through the skin beneath the mold.
  • a severe breakout can encase portions of the machine that are in its path in molten metal, rendering those components unusable and requiring them to be replaced and reconditioned.
  • One of the factors that is important in determining whether or not a breakout is likely to occur is the thickness of the skin as the casting moves though the mold. Theoretically, skin thickness could be measured in situ during casting by monitoring the infrared emissions of the slab, but in practice this has not been feasible because the entire slab is surrounded by the mold, making
  • JP 62 130748 discloses a water-cooled mold with a ceramic liner to improve wear resistance and durability.
  • the inold's liner is composed of boron nitride of a thermal conductivity greater than or equal to 50 W/mK.
  • the mold is not in the field of continuous casting however.
  • a mold for casting aluminium is shown in WO98/16335 and consists of mold wall assemblies having an inner portion arranged to conduct heat away from the mold liner, and an outer portion coated with boron nitride or diamond.
  • an improved mold wall assembly for use in a continuous casting machine is provided as defined in claim 1 below.
  • a preferred embodiment comprising continuous casting machine is defined in claim 7.
  • a method of making a strand of continuously cast material in accordance with claim 8 below.
  • an improved mold wall assembly 12 for a continuous casting machine 10 includes a plurality of mold walls, including an opposing pair 14, 16 of narrowface walls and an opposing pair of broadface walls 18,20.
  • Each of the mold walls 14, 16, 18, 20 has at least one mold surface that together define a casting space 26 having an upper opening and a lower opening.
  • the mold wall assembly 12 is designed, as is conventional, so that molten metal can be supplied continuously into the top end of the casting space 26, and so as to cool the metal so that an outer skin forms before the so-formed slab or strand exits a bottom of the casting passage.
  • coolant supply pipes 22, 24 are provided for providing a water coolant to the narrowface walls 14, 16 and the broadface walls 18, 20, respectively.
  • FIGURE 2 is a vertical cross-sectional view taken through one of the broad face walls 20 in FIGURE 1, it will be seen that wall 20 includes a liner assembly 27 that bears the mold face 28, and a support assembly 32 to which the liner assembly 27 is secured.
  • the liner assembly 27 includes an inner portion 29 that is embodied as a copper liner 30, and an outer layer 44 of degradation-resistant, non-metallic material that forms the mold face 28, and will be discussed in greater detail below.
  • the support assembly 32 includes the coolant supply pipe 24, a coolant return pipe 42, an inlet plenum 36 and an outlet plenum 38.
  • Both the inlet and outlet plenums 36, 38 are in communication with a cooling channel 34 that is defined in the copper liner 30 of the liner assembly 27.
  • the coolant which is typically water
  • the coolant is introduced from the coolant supply pipe 24 into the inlet plenum 36, where it flows upwardly through the cooling channel 34 and out into the outlet plenum 38.
  • the coolant is then returned to a circulation pump through the return pipe 42.
  • the layer 44 of degradation-resistant, non-metallic material is diamond or cubic boron nitride. These materials preferably a are efficient conductors of heat, that are very hard and degradation-resistant, that can tolerate the high temperatures that exist in a continuous casting mold during operation, that are resistant to the acidic environment in which a continuous casting machine typically functions, and that, for reasons discussed in greater detail below, are transparent in the infrared portion of the spectrum.
  • Diamond is a allotrope of carbon that is metastable at ordinary pressures, having a large activation energy barrier that prevents conversion to graphite, the more stable allotrope at ordinary temperatures and pressures. It has long been sought after not only for its intrinsic beauty and value as a gemstone but also for its many unique and valuable mechanical, electrical, optical and thermal properties. Diamond is the hardest material occurring in nature, has a low co-efficient of friction, is extremely resistant to chemical attack, is optically transparent to much of the electromagnetic spectrum, including being highly transparent to infrared radiation, and has the highest heat conductivity of any material. Cubic boron nitride (CBN) has properties that are comparable to diamond in many respects.
  • FIGURE 3 One advantageous feature of the invention is depicted diagrammatically in FIGURE 3.
  • a passage 46 is formed in the copper liner plate 30 of the liner assembly 27.
  • An optical fiber 48 is situated in the passage 46, and is optically coupled to the transparent layer 34 of degradation-resistant, non-metallic material on a side thereof that is opposite to the casting surface or mold face 28 of the layer 44.
  • a sensor 50 is then coupled to a second, opposite end of the optical fiber 48. The purpose of the sensor 50 is to monitor a property of the continuous casting process by examining the spectral characteristics of the light that is carried through the optical fiber 48.
  • sensor 50 is constructed and arranged to monitor the infrared profile of the transmitted light, so as to monitor the temperature of the exterior of the cast strand as it moves downwardly along the casting surface within the mold. By monitoring this temperature, the thickness of the skin of the casting can be determined, which is a useful indicator for many things, including the susceptibility of the strand to breakouts after it exits the bottom of the mold, the optimal withdrawal speed of the strand from the machine, the optimal rate at which coolant is circulated through the mold walls, and the uniformity of shell growth.
  • FIGURE 4 it will be seen that a number of such sensors 50 are provided in the mold assembly, and that each of those sensors provides information to a CPU 52 that serves as a local control system for the mold wall assembly 12.
  • CPU 52 is in two-way communication with a main control system 54 of the continuous casting machine 10, and is further in communication with different subsystems for modifying different performance variables of the continuous casting process.
  • FIGURE 4 depicts four such subsystems 56, 58, 60 , 62, but the number could be more or less, depending upon the number of performance variables that are desired to be controlled in response to the optical monitoring that is performed by the sensor 50.
  • one of the subsystems may permit adjustment of the withdrawal speed of the continuous casting machine.
  • Another subsystem may permit adjustment of the taper of the mold.
  • Third and fourth subsystems for adjusting the rate of cooling the mold may constitute a control system for adjusting the volumetric flow of coolant through one or more of the mold walls, or changing the composition of mold flux for changing the heat conduction properties of the mold.
  • thermal imaging system In order to analyze the data that is gathered by the sensors 50, a commercially available thermal imaging system may be used.
  • One such imaging system that could be used is available from Mikron Instruments of Oakland, New Jersey and is sold as an "Imaging Pyrometer.” This system is disclosed in part in U.S. Patent 4,687,344, the disclosure of which is hereby incorporated as if set forth fully herein.
  • a mold assembly 64 that is constructed according to a second embodiment of the invention includes a casting surface 66, and a body 68 that is fabricated entirely of the non-metallic, degradation-resistant material of the type that is discussed in detail above.
  • a cooling channel 70 is defined in the body 68 of material, and a sensor 72, which is similar in construction to the sensor 50 discussed above, is coupled to a rear side of the body 68.
  • the entire mold wall is made of the diamond or CBN material. It is believed that this embodiment holds great potential for the future, because such a mold wall would be expected to substantially outperform any mold wall that is in service today. Fabricated entirely of a material such as diamond, it would be much more efficient at conducting heat away from the strand during casting than a metallic mold wall would, it would exhibit lower friction than any metallic mold wall would, and it would be virtually indestructible in terms of wear.
  • FIGURE 6 depicts yet another embodiment of the invention.
  • the entire mold liner 80 is fabricated from a degradation-resistant nonmetallic material that has high thermal conductivity, whereby the mold liner will exhibit superior wear and heat transfer characteristics during its operation in a continuous casting machine.
  • the preferred materials are diamond or CBN, and the mold liner can be constructed according to any of the fabrication processes disclosed below, or by any other process that will be effective.
  • a sensor 72 which is similar in construction to the sensor 50 discussed above, is coupled to a rear side of the mold liner 80.
  • the mold liner 80 does not have an internal cooling passage, but is constructed as a "spray-type" mold in which the side 86 of the liner that is opposite the casting 82 is subjected to cooling spray from one or more spray nozzles 88.
  • the high thermal conductivity of this type of mold liner will contribute to the effective cooling of the casting and the formation of casting that has a uniform solidified shell 84.
  • a significant amount of heat will also be transferred away from the casting by means of radiation as a result of the transparency of the mold in the infrared range. This stands in favorable contrast to a conventional continuous casting mold, where there is no heat transfer through the mold wall by means of radiation.
  • a diamond-like carbon film can be deposited in the surface of a substrate by exposing the surface to an argon ion beam containing a hydrocarbon.
  • the current density in the ion beam is low during initial deposition of the film.
  • the ion beam is increased to full power.
  • a second argon ion beam is directed toward the surface of the substrate.
  • the second ion beam has an energy level much greater than that of the ion beam containing the hydrocarbon.
  • an amorphous, carbonaceous, diamond-like film is produced by a hybrid process in a deposition chamber using a radio frequency plasma decomposition from an alkane, such as n-butane, using a pair of spaced, generally parallel, carbon electrodes, preferably ultra pure carbon electrodes. While most films of this invention were deposited using normal butane, other alkanes, such as methane, ethane, propane, pentane, and hexane can be substituted in the process of this invention to produce the improved carbonaceous, diamond-like film thereof.
  • the deposition chamber such as a stainless steel chamber, includes a pair of generally parallel and horizontal, vertically spaced, pure carbon electrodes with the substrate to be coated positioned on the lower carbon electrode.
  • the electrodes are typically positioned about 2 up to about 8 centimeters apart from each other, with the preferred electrode spacing being approximately 2.5 centimeters.
  • the chamber is evacuated to its ultimate pressure, generally in the region of about 10 ⁇ - 7 > torr, and then backfilled with an alkane, such as n-butane, to a pressure of approximately 8 x 10 ⁇ - 4 > torr. Thereafter, the vacuum system is throttled to a pressure in the range of approximately 25 to 100 millitorr.
  • the radio frequency power is applied to the pair of pure carbon electrodes with the lower electrode (substrate target) being biased in the range of about 0 to about - 100 volts, and the upper electrode being biased in the range of about - 200 to about - 3500 volts.
  • Radio frequency plasma decomposition is begun, and an amorphous, carbonaceous, diamond-like film is deposited onto the substrate at rates varying between about 8 up to 35 angstroms per minute, to produce a film of up to about 5 micrometers in thickness.
  • a hard carbonaceous film is formed by decomposing a gaseous hydrocarbon having carbon atoms tetrahedrally coordinated to its nearest neighbors through carbon-carbon single bonds.
  • the gaseous hydrocarbon is decomposed in a radio frequency maintained plasma and the plasma decomposition products are deposited on a cathodic substrate.
  • fluorocarbons may be present in a decomposition gas.
  • a hydrocarbon/hydrogen gas mixture is passed through a refractory metal hollow cathode which is self heated to a high temperature.
  • the gas mixture is dissociated by a combination of thermal and plasma effects.
  • the plasma plume emanating from the hollow cathode heats the substrate, which is positioned on a surface of the anode. Growth of the diamond film is enhanced by bombardment of electrons.
  • a film is formed on a substrate through a process of bringing a substrate into contact with a plasma zone formed by generating, by use of a discharge electrode or discharge electrodes, high temperature or quasi-high temperature plasma of a gas containing at least one carbon-containing compound.
  • the electrodes include a sheet-like electrode provided with a slit having a linear portion and connected to a microwave electric source.
  • the plasma zone is formed by forcing a high temperature or quasi-high temperature plasma generated in an arc between the electrodes to move by applying a magnetic field. The process enables energy efficient formation of films on substrate surfaces.
  • a synthetic diamond film may be formed by a D.C. plasma-assisted deposition at 0.5 to 1.5 amperes plasma current at a temperature of 600 to 800 degrees C using methane/ hydrogen (0.8-1 : 99.5-1 volume ratio) at a total pressure of 20-30 torr.
  • diamond films are deposited at substrates below temperatures of 400 degrees C. by chemical vapor deposition using a high powered pulsed laser and a vapor which is an aliphatic carboxylic acid or an aromatic carboxylic anhydride.
  • a thin diamond film is prepared by immersing a substrate in a liquid containing carbon and hydrogen and then subjecting the substrate to at least one laser pulse.
  • a method of depositing diamond-like films produces depositing species from a plasma of a hydrocarbon gas precursor.
  • the plasma is generated by a laser pulse, which is fired into the gas and is absorbed in an initiater mixed with the gas.
  • the resulting detonation produces a plasma of ions, radicals, molecular fragments and electrons which is propelled by the detonation pressure wave to a substrate and deposited thereon.
  • the apparatus includes a vacuum chamber containing a target material and a laser focused on the target to ablate the material and ionize a portion of the ablation plume.
  • An accelerating grid within the vacuum chamber is charged to extract the ions from the plume and direct the ions onto a substrate to grow the layer.
  • the basic embodiment has produced diamond-like carbon films on a clean, unseeded silicon substrate at deposition rates approaching 20 microns per hour.
  • the diamond-like carbon films produced were of exceptional quality: uniform thickness with a surface roughness about 1 Angstrom; uniform index of refraction within the range of 1.5-2.5; resistivity greater than 40 megs ohms per centimeter; and a hard surface resistant to physical abuse.
  • An enhanced embodiment includes multiple targets within the vacuum chamber and mechanisms to selectively produce ions from each target. Thus, layers of different materials or doped materials can be made on the substrate. Additionally, the enhanced embodiment includes a mechanism for making patterns or circuits within each layer.
  • One version incorporates a mask within the ion fluence and ion optics to magnify the mask pattern onto the substrate.
  • Another version uses ion optics to form an ion beam and deflection plates controlling the ion beam to write the desired pattern on the substrate.
  • a process for forming synthetic diamond which involves vapor deposition of a carbon gas source in the presence of atomic hydrogen on a substrate contained in a fluidized bed.
  • the diamond may be overcoated by vapor deposition of a non-diamond material.
  • a method for depositing diamond films and particles on a variety of substrates by flowing a gas or gas mixture capable of supplying (1) carbon, (2) hydrogen and (3) a halogen through a reactor over the substrate material.
  • the reactant gases may be pre-mixed with an inert gas in order to keep the overall gas mixture composition low in volume percent of carbon and rich in hydrogen.
  • Pre-treatment of the reactant gases to a high energy state is not required as it is in most prior art processes for chemical vapor deposition of diamond. Since pre-treatment is not required, the may be applied to substrates of virtually any desired size, shape or configuration.
  • the reactant gas mixture preferably is passed through a reactor, a first portion of which is heated to a temperature of from about 400 degrees C. to about 920 degrees C. and more preferably from about 800 degrees C. to about 920 degrees C.
  • the substrate on which the diamond is to be grown is placed in the reactor in a zone that is maintained at a lower temperature of from about 250 degrees C. to about 750 degrees C., which is the preferred diamond growth temperature range.
  • the process preferably is practiced at ambient pressures, although lower or higher pressures may be used. Significant amounts of pure diamond films and particles have been obtained in as little as eight hours. The purity of the diamond films and particles has been verified by Raman spectroscopy and powder x-ray diffraction techniques.
  • thin films of single crystal, cubic phase boron nitride that is epitaxially oriented upon a silicon substrate are formed using laser ablation techniques.
  • a method of forming a polycrystalline film, such as a diamond, on a foreign substrate involves preparing the substrate before film deposition to define discrete nucleation sites.
  • the substrate is prepared for film deposition by forming a pattern of irregularities in the surface thereof.
  • the irregularities typically craters, are arranged in a predetermined pattern, which corresponds to that desired for the location of film crystals.
  • the craters preferably are of uniform, predetermined dimensions (in the sub-micron and micron size range) and are uniformly spaced apart by a predetermined distance.
  • the craters may be formed by a number of techniques, including focused ion beam milling, laser vaporization, and chemical or plasma etching using a patterned photoresist.
  • the film may be deposited by a number of known techniques. Films prepared by this method are characterized by a regular surface pattern of crystals, which may be arranged in virtually any desired pattern.
  • a highly pure cubic boron nitride film is formed on a substrate by a method which involves irradiating an excimer laser on a target comprising boron atoms and optionally nitrogen atom and depositing cubic boron nitride on a substrate which is placed to face the target.
  • infrared lasers are used to deposit diamond thin films onto a substrate.
  • the deposition of the film is from a gas mixture of CH4 and H2 that is introduced into a chemical vapor deposition chamber and caused to flow over the surface of the substrate to be coated while the laser is directed onto the surface.
  • pure carbon in the form of soot is delivered onto the surface to be coated and the laser beam is directed onto the surface in an atmosphere that prevents the carbon from being burned to CO2.
  • a method for developing diamond thin films on a non-diamond substrate involves implanting carbon ions in a lattice-plane matched or lattice matched substrate. The implanted region of the substrate is then annealed to produce a diamond thin film on the non-diamond substrate. Also disclosed are the diamond thin films on non-diamond lattice-plane matched substrates produced by this method.
  • Preferred substrates are lattice and plane matched to diamond such as copper, a preferred implanting method is ion implantation, and a preferred annealing method is pulsed laser annealing.
  • a method of producing transparent diamond laminates which employs a substrate which is removed once a second layer is deposited over the diamond coating, thereby exposing a smooth diamond surface.
  • the second coating should have a refractive index substantially identical to diamond, with zinc selenide and titanium dioxide being particularly preferred.
  • Diamond films having two smooth surfaces may be produced by simultaneous deposition on parallel, opposed substrates until the two diamond films merge together to form a single film or plate, followed by removal of at least a portion of the two substrates.
  • a diamond film or an I-Carbon film is formed on a surface of an object by virtue of plasma-assisted chemical vapor deposition.
  • the hardness of the films can be enhanced by applying a bias voltage to the object during deposition.
  • a cemented tungsten carbide substrate is prepared for coating with a layer of diamond film by subjecting the substrate surface to be coated to a process which first removes a small amount of the tungsten carbide at the surface of the substrate while leaving the cobalt binder substantially intact.
  • Murakami's reagent is presently preferred.
  • the substrate is then subjected to a process, which removes any residue remaining on the surface as a result of the performance of the process, which removes the tungsten carbide.
  • a solution of sulfuric acid and hydrogen peroxide is presently preferred.
  • a diamond coated cemented tungsten carbide tool is formed using an unpolished substrate, which may be prepared by etching as described above or by etching in nitric acid prior to diamond film deposition.
  • Deposition of a substantially continuous diamond film may be accomplished by reactive vapor deposition, thermally assisted (hot filament) CVD, plasma-enhanced CVD, or other techniques.
  • a method for providing a coating film of diamond on a substrate involves the plasma jet deposition method, in which the deposited diamond film has, different from the cubic crystalline structure formed under conventional conditions, a predominantly hexagonal crystalline structure so as to greatly enhance the advantages obtained by the diamond coating of the tool in respect of the hardness and smoothness of the coated surface.
  • the improvement comprises: using hydrogen alone as the plasma-generating gas; controlling the pressure of the plasma atmosphere not to exceed 300 Torr; keeping the substrate surface at a temperature of 800 degrees-1200 degrees C.; and making a temperature gradient of at least 13,000 degrees C./cm within the boundary layer on the substrate surface.
  • a diamond film is attached securely to the substrate by forming a first layer on the surface comprising a mixture of a main component of the substrate and a sintering reinforcement agent for diamond, then forming a second layer comprising a mixture of said agent and diamond on said first layer, and finally forming the diamond film on the second layer.
  • the bond strength between a diamond and the substrate onto which it is deposited by the chemical vaporization method is decreased to the point where the diamond can be removed from the substrate as a free standing monolithic sheet.
  • the bond strength can be decreased by polishing the substrate, removing comers from the substrate, slow cooling of the substrate after deposition, an intermediate temperature delay in cooling or the application or formation of an intermediate layer between the diamond and the substrate.
  • the freestanding sheet of diamond is envisioned as being of particular use for the embodiment of FIGURE 5.
  • a coating film of a carbon allotrope is formed on a substrate by continuously supplying a fine carbon powder onto the substrate and simultaneously irradiating the fine carbon powder with a laser beam of a high output level thereby inducing sublimation of the fine carbon powder, and quenching the sublimated fine carbon powder to cause deposition thereof on the substrate.
  • a substantially transparent polycrystalline diamond film is made having a thickness greater than 50 microns.
  • a mixture of hydrogen and methane is conveyed into a heat filament reaction zone, which is adjacent to an appropriate substrate, such as a molybdenum substrate to produce non-adherent polycrystalline substantially transparent diamond film.
  • a layer of a hydrocarbon molecule is applied to a substrate by the Langmuir-Blodgett technique, and the surface is irradiated with a laser to decompose the layer of molecules at the surface without influencing the substrate. After decomposition the carbon atoms rearrange on the surface of the substrate to form a DLC film.
  • a method for growing diamond on a diamond substrate by chemical vapor deposition involves alternatingly contacting at elevated temperature said diamond substrate with a gas having the formula Cn X m and then with a gas having the formula C 1 Z p .
  • X and Z each form single bonds with carbon.
  • X and Z also are reactable to form ZX or a derivative thereof.
  • the Z-X bond is stronger than the C-X bond and also is stronger than the C-Z bond.
  • n, m, 1, and p are integers.
  • diamond materials are formed by sandwiching a carbon-containing material in a gap between two electrodes.
  • a high-amperage electric current is applied between the two electrode plates so as cause rapid heating of the carbon-containing material.
  • the current is sufficient to cause heating of the carbon-containing material at a rate of at least approximately 5,000 degrees C./sec, and need only be applied for a fraction of a second to elevate the temperature of the carbon-containing material at least approximately 1000 degrees C.
  • the carbon-containing material is subjected to rapid-quenching (cooling).
  • the carbon-containing material may be rapidly-heated and rapidly-quenched (RHRQ) repeatedly (e.g., in cycles), until a diamond material is fabricated from the carbon-containing material.
  • RHRQ rapid-heated and rapidly-quenched
  • the process is advantageously performed in an environment of a "shielding" (inert or non-oxidizing) gas, such as Argon (At), Helium (He), or Nitrogen (N2).
  • the carbon-containing material is polystyrene (e.g., a film) or glassy carbon (e.g., film or powder).
  • the carbon-containing material is a polymer, fullerene, amorphous carbon, graphite, or the like.
  • One of the electrodes is preferably a substrate upon which it is desired to form a diamond coating, and the substrate itself is used as one of the two electrodes.
  • a continuous diamond structure deposited by chemical vapor deposition having at least two thermal conductivity diamond layers controlled by the diamond growth rate where one thermal conductivity diamond layer is grown at a high growth rate of at least one micron per hour for hot filament chemical vapor deposition and at least 2-3 microns per hour for microwave plasma assisted chemical vapor deposition, on a substrate such as molybdenum in a chemical vapor deposition chamber and at a substrate temperature that promotes the high growth rate, and the other thermal conductivity diamond layer is grown at a growth rate and substrate temperature lower than the high growth rate diamond layer.
  • High growth rate and low growth rate diamond layers can be deposited in any sequence to obtain a continuous diamond structure that does not show distinguishable, separate, crystalline columnar layers, having improved thermal conductivity.
  • energy such as from a UV excimer laser, an infrared Nd:YAG laser and an infrared CO 2 laser is directed through a nozzle at the surface of a substrate to mobilize and vaporize a carbon constituent (e.g. carbide) within the substrate (e.g. steel).
  • a carbon constituent e.g. carbide
  • An additional secondary source e.g. a carbon-containing gas, such as CO 2
  • an inert shielding gas e.g. N 2
  • the vaporized constituent element is reacted by the energy to alter its physical structure (e.g. from carbon to diamond) to that of a composite material, which is diffused into the back of the substrate as a composite material.
  • laser energy is directed at a substrate to mobilize, vaporize and react a constituent (primary) element (e.g. carbon) contained within the substrate. so as to modify the composition (e.g. crystalline structure) of the constituent element, and to diffuse the modified constituent back into the substrate, as an adjunct to fabricating a coating (e.g. diamond or diamond-like carbon) on the surface of the substrate.
  • a constituent element e.g. carbon
  • Additional (secondary) similar (e.g. carbon) or dissimilar elements may be introduced in a reaction zone on and above the surface of the substrate to augment the fabrication of and to determine the composition of the coating.
  • the laser energy is provided by a combination of an excimer laser, an Nd: YAG laser and a CO 2 laser, the output beams of which are preferably directed through a nozzle delivering the secondary element to the reaction zone.
  • the reaction zone is shielded by an inert (non-reactive) shielding gas (e.g.
  • a flat plasma is created by the lasers, constituent element and secondary element on the surface of the substrate and the flat plasma optionally extends around the edges of the substrate to fabricate a coating thereon.
  • Pre-treatment and coating fabrication can be preformed in conjunction with one another (in-situ). Alternatively, a substrate can be pre-treated to characterize its surface for subsequent coating. In either case, certain advantageous metallurgical changes are induced in the substrate due to the pre-treatment.
  • the processes (pre-treatment and coating fabrication) are suitably performed in ambient, without preheating the substrate and without a vacuum.
  • the lasers are directed at any suitable angle (including coaxial) relative to the substrate and/or the plasma.

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  • Engineering & Computer Science (AREA)
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  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
  • Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
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  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
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  • Continuous Casting (AREA)
  • Mold Materials And Core Materials (AREA)
EP99938971A 1998-08-06 1999-08-04 An improved continuous casting mold system and related processes Expired - Lifetime EP1019209B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US130144 1987-12-08
US13014498A 1998-08-06 1998-08-06
PCT/US1999/017602 WO2000007752A1 (en) 1998-08-06 1999-08-04 An improved continuous casting mold system and related processes

Publications (2)

Publication Number Publication Date
EP1019209A1 EP1019209A1 (en) 2000-07-19
EP1019209B1 true EP1019209B1 (en) 2004-12-08

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP99938971A Expired - Lifetime EP1019209B1 (en) 1998-08-06 1999-08-04 An improved continuous casting mold system and related processes

Country Status (10)

Country Link
EP (1) EP1019209B1 (zh)
JP (1) JP2002522225A (zh)
KR (1) KR20010024423A (zh)
CN (1) CN1275101A (zh)
AT (1) ATE284282T1 (zh)
AU (1) AU5334399A (zh)
BR (1) BR9906674A (zh)
CA (1) CA2305188A1 (zh)
DE (1) DE69922479T2 (zh)
WO (1) WO2000007752A1 (zh)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007157962A (ja) * 2005-12-05 2007-06-21 Sumitomo Electric Ind Ltd 型成形工具
DE102009037283A1 (de) * 2009-08-14 2011-02-17 Kme Germany Ag & Co. Kg Gießform
ITUD20130090A1 (it) * 2013-06-28 2014-12-29 Danieli Off Mecc Cristallizzatore per colata continua e procedimento per la sua realizzazione
DE102014218449A1 (de) * 2014-09-15 2016-03-17 Schunk Kohlenstofftechnik Gmbh Gussform und Verfahren zur Herstellung
IT201900010347A1 (it) * 2019-06-28 2020-12-28 Danieli Off Mecc Cristallizzatore per la colata continua di un prodotto metallico e relativo procedimento di colata
CN111039256B (zh) * 2019-12-12 2022-07-22 江苏大学 一种用于制备纳米层状复合材料的模具及方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59147751A (ja) * 1983-02-09 1984-08-24 Sumitomo Electric Ind Ltd 連続鋳造圧延方法
JPS62130748A (ja) * 1985-11-29 1987-06-13 Toshiba Corp 耐摩耗性水冷モ−ルド部品
US4687344A (en) * 1986-02-05 1987-08-18 General Electric Company Imaging pyrometer
US4954365A (en) * 1989-12-18 1990-09-04 The United States Of America As Represented By The Secretary Of The Army Method of preparing a thin diamond film
US5499672A (en) 1994-06-01 1996-03-19 Chuetsu Metal Works Co., Ltd. Mold for continuous casting which comprises a flame sprayed coating layer of a tungsten carbide-based wear-resistant material

Also Published As

Publication number Publication date
CA2305188A1 (en) 2000-02-17
EP1019209A1 (en) 2000-07-19
CN1275101A (zh) 2000-11-29
KR20010024423A (ko) 2001-03-26
JP2002522225A (ja) 2002-07-23
WO2000007752A1 (en) 2000-02-17
DE69922479T2 (de) 2005-05-12
WO2000007752A9 (en) 2000-10-05
BR9906674A (pt) 2000-11-07
AU5334399A (en) 2000-02-28
DE69922479D1 (de) 2005-01-13
ATE284282T1 (de) 2004-12-15

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