US3892890A - Process for forming carbon coatings - Google Patents

Process for forming carbon coatings Download PDF

Info

Publication number
US3892890A
US3892890A US358647A US35864773A US3892890A US 3892890 A US3892890 A US 3892890A US 358647 A US358647 A US 358647A US 35864773 A US35864773 A US 35864773A US 3892890 A US3892890 A US 3892890A
Authority
US
United States
Prior art keywords
gas
process according
nickel
carbon
alloy layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US358647A
Other languages
English (en)
Inventor
Kiyoshi Watanabe
Akira Misumi
Takayoshi Onodera
Kazuo Sunahara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP47046396A external-priority patent/JPS5143038B2/ja
Priority claimed from JP47046395A external-priority patent/JPS5129718B2/ja
Priority claimed from JP47046394A external-priority patent/JPS5143037B2/ja
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Application granted granted Critical
Publication of US3892890A publication Critical patent/US3892890A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26Deposition of carbon only
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02Pretreatment of the material to be coated
    • C23C16/0272Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C23C16/0281Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers

Definitions

  • ABSTRACT A nickel-phosphorus alloy layer having an amount of 4-12 percent by weight phosphorus is first allowed to adhere to the surface of a substrate and the nickelphosphorus alloy layer-coated substrate is heated in an atmosphere of a noncombustible hydrocarboncontaining gas to effect thermal decomposition of the gas, thereby depositing carbon onto the surface of said substrate to form a dense carbon coating thereon without causing thermal deformation of the coated substrate or decrease in stiffness of the resulting carbon coating. It is also possible to first subject a nickelphosphorus alloy layer formed on the surface of a substrate to preliminary oxidation and then heat the substrate in the presence of a hydrocarbon-containing gas to effect thermal decomposition of said gas.
  • This invention relates to a process for forming a graphitic carbon coating at relatively low temperatures on the surface of an object composed of a metal or other material. More particularly, the invention pertains to a novel and efficient process for forming a carbon coating at a relatively low temperature below 700C on the surface of an object (hereinafter referred to as substrate") composed of such metal. for example. as an iron sheet or other substance in such a state that the carbon coating formed has a predetermined thickness, is high in density, and is firmly stuck to the surface of the substrate.
  • Carbon has not only exellent corrosion resistance to chemical agents but also good physical properties such as heat radiation ability. Carbon is also low in secondary-electron emission. and hence in the field of electronic appliances and parts thereof. those appliances or parts are frequently used after being coated on the surface thereof with carbon with the view of preventing said surface from secondary-electron emission.
  • a process for coating the surface of substrates with carbon is roughly divided into three methods. i.e. spreading, evaporating or spattering. and decomposing.
  • the spreading method i.e. the first one of the abovementioned three methods. is to spread or spray a carbon-containing paint on a substrate. This method is very simple.
  • the said method has also such drawback that because of weak adhesion between the substrate and the spread carbon layer, in the spread substrate obtained by this method the carbon layer easily peels off from the substrate when said substrate is heat-treated.
  • This method is not a practical means to obtain a uniform and dense carbon layer on the surface of substrate.
  • As the second method there is a vacuum evaporation coating. According to this method, a dense and strongly adhesive carbon coating can be obtained. In order to evaporate and deposit carbon in vacuo. it is necessary to maintain the temperature of carbon necessary therefor at a high temperature of at least 2.500C In the case where treatment of a large number of substrates relatively large in size is intended to be carried out economically.
  • anode of receiving tube is coated with carbon with the view of maximizing heat radiation
  • the anode is heated in vacuo at any temperatures between about 600 and about 900C. and the heating is repeated.
  • the condition under which the shadow mask is used is such that the use of inorganic type binders having characteristics to promote secondary-electron emission is absolutely not permissible. and also there is required such adhesive strength of the carbon coating that said coating is not substantially worn by combustion even when heated in air at a temperature of about 400 to 500C for l to 2 hours. and even when the coating has a thickness of about 1 micron or thicker.
  • a graphite coating is preferably used so that the coating may not peel off from the boat due to mechanical rubbing during operation at an elevated temperature.
  • a graphite coating deposited on a substrate by thermal decomposition of a graphitic carbon-containing reaction gas is most preferable as the graphite coating as mentioned above. which does not substantially subject to loss in weight even when heated in vacuo and/or scrubbed mechanically or heated in air at a temperature of about 400 to about 500C. and which does not also peel off from a substrate even placed in such state that neither organic nor inorganic binders can be used. and which does not produce carbon dusts.
  • the third method there is a method in which a carbon-containing gas is allowed to react under heating to deposit carbon. thereby coating a substrate with the depositing carbon.
  • the carbon coating formed on the substrate strongly sticks to the substrate and is high in density.
  • This method is widely used in general.
  • the greatest drawback of this method. however. is that the carbon coating is formed by thermal reaction wherein a substrate is heated in the presence of the reactive gas stream comprising methane. propane. etc. at such elevated temperature as high as l ,200 to 2000 C. Because of such high heating temperatures employed in this method, when a substrate is a thin metallic sheet or a material low in heat resisting property. the carbon-coated substrate suffers from its deformation or change in quality of the substrate itself.
  • a substrate is a material which is sufficiently resistant to the aforesaid temperature.
  • the substrate is liable to damages such as thermal deformation because it is heated at high temperature.
  • the heating temperature employed therefor should be suppressed at least to 700C or below.
  • this method is to coat the very porous nickel disc formed from nickel powder on its surface with carbon. and hence this method cannot be applied at all. for example. to the case where such a sheet as a thin iron sheet having a thickness of 0.5 mm or less is intended to be coated on its surface with carbon high in accuracy.
  • a primary object of the present invention is to provide a novel and effective process in which the surface of substrate such as an iron sheet may be coated with a dense carbon to form thereon without forming any carbide on the surface of the substrate and without bringing about such disadvantages as thermal deformation of the coated substrate or decrease in stiffness of the resulting carbon coating.
  • Another object of the present invention is to provide a process in which a carbon-containing gas is allowed to react at a relatively low temperature of about 700C or below. thereby forming on the surface of a substrate a dense carbon coating having a firm adhesion between said carbon coating and the surface of the substrate.
  • Another object of the present invention is to provide a process. according to which even the surface of a thin iron sheet substrate having a thickness of about 0.5 mm or less with carbon to form thereon a carbon coating having a thickness of l mg/cm' with uniformity and with accuracy.
  • said carbon coating being extremely high in density. having a carbon density of about 1.9 g/cm. and having a high adhesive strength so that said carbon coating does not peel off from the surface of the substrate even when subjected to quick heating and cooling tests at a temperature of 600C or below.
  • the present inventors have found that in a process for depositing carbon on the surface of a substrate by the reaction of a hydrocarbon-containing gas the above-mentioned objects can be accomplished by pre viously forming a suitable catalyst material on the surface of the substrate. thereby depositing carbon utilizing a strong catalytic action of said catalyst material to form a dense carbon coating which adheres strongly to the surface of the substrate.
  • FIG. 1 is a graph showing the relationship between a pH value of a nickel-phosphorus alloy plating solution and an amount of phosphorus contained in the nickelphosphorus alloy layer obtained from said plating solution.
  • FIG. 2 is a sketch showing an example of the manufacturing apparatus illustrating a process for preparing a carbon coating.
  • FIG. 3 is a graph showing the relationship between an amount of phosphorus contained in the nickelphosphorus alloy layer. an amount of carbon deposited. and a porosity of carbon.
  • FIG. 4 is a graph showing the relationship between an amount of carbon deposited and a treatment time.
  • FIG. 5 is a graph showing the relationship between a Liquefied Petroleum Gas (hereinafter referred to as L.P.G.”) concentration in the reactive gas and an amount of carbon deposited.
  • L.P.G. Liquefied Petroleum Gas
  • FIG. 6 is a graph showing the relationship between an acetylene concentration in the reactive gas and an amount of carbon deposited.
  • FIG. 7 is a graph showing the relationship between a preliminary heating time at 600C of a nickel phosphorus alloy layer and an amount of deposited carbon resulting from a thermal decomposition reaction of acetylene gas.
  • FIG. 8 is a graph showing the relationship between partial pressures of the resulting hydrogen associated with thermal decomposition of a sample having a catalytic action and a sample which lost its catalytic action in an atmosphere of acetylene gas, and a heat reaction time.
  • FIG. 9 is a graph showing the relationship between amounts of carbon deposited when an iron sheet substrate plated on its surface with a nickel-phosphorus alloy as a catalyst is heated in an atmosphere of each of the three reaction gases having different compositions. and heating temperature.
  • FIG. is a graph showing an amount of carbon deposited and an amount of phosphorus contained in a nickel-phosphorus alloy layer having a thickness of about one micron formed on the surface of an iron sheet substrate.
  • FIG. 11 is a graph showing the relationship between a concentration of oxygen in a nitrogen stream and an amount of carbon deposited in the case where an iron sheet substrate is plated on the surface with a nickelphosphorus alloy to form a layer thereof having a thickness of one micron and then this nickel-phosphorus alloy layer is subjected to a preliminary oxidation treatment in a nitrogen oxygen atmosphere at about 600C for 10 minutes.
  • the present invention intends to coat the surface of a substrate such as a thin iron sheet or a heat resistant material with a dense carbon film having a firm adhesion force, to the substrate by effecting reaction of a hydrocarbon-containing gas at a low heat treatment temperature such as 700C or below, which temperature was not conceivable at all in the prior art processes. It is impossible to deposit on the surface of a substrate by merely effecting a reaction of a carbon-containing gas at such low temperature as intended in the present invention. As explained previously, in order to accomplish this object, it is necessary to utilize a strong catalytic action of a material formed on the surface ofa substrate intended to be coated with carbon. The present inventors conducted experiments.
  • process of the present invention is based on the above finding, wherein the surface of a substrate is plated with a nickelphosphorus alloy having an appropriate composition and the thus plated substrate is heated in a gas atmosphere comprising a predetermined amount of a hydrocarbon gas up to a predetermined reaction temperature within the range from 450 to 700C preferably within a fixed time to carry out the reaction under heating, thereby forming a dense carbon coating on the surface of said substrate.
  • a gas atmosphere comprising a predetermined amount of a hydrocarbon gas up to a predetermined reaction temperature within the range from 450 to 700C preferably within a fixed time to carry out the reaction under heating, thereby forming a dense carbon coating on the surface of said substrate.
  • Acetylene gas is, as is well known, one of the most unstable gases among hydrocarbon gases, and is large in change of free energy associated with the decomposition thereof within a relatively low temperature range such as about l,000C or below. That is, generally at a low temperature of about lO00C or below (hereinafter referred to as low temperature"), acetylene gas belongs to those which are most liable to thermal decomposition among hydrocarbon gases.
  • the reaction of acetylene is an exothermic reaction and, it is represented, for example, at room temperature by the following equations.
  • acetylene gas in order to make it possible to effect selectively a thermal decomposition of acetylene gas in a controlled atmosphere comprising acetylene gas at a relatively low temperature in the presence of an optional substrate, thereby depositing carbon on the surface of the substrate to form thereon a stable crystalline carbon film, it is most effective to coat the surface of said substrate under the conditions as explained previously with a catalyst material which will act in response to the progress of the selective thermal decomposition reaction of acetylene gas.
  • catalyst material is preferably a material which can be coated on the surface of an optional substrate in a simple as well as an economical manner.
  • the present invention has been made with an eye to various problems: such technical difficulties associated with prior art processes as illustrated in detail previously, characteristics of the thermal decomposition reaction of acetylene gas. utilization of the catalyst material as a countermeasure relative to the acetylene gas reaction and so on. Accordingly, the present invention, as explained previously, is to provide a novel process for coating the surface of a substrate with a crystalline carbon layer which is dense and having a high adhesion strength in a safe and stabilized operational condition by utilizing a catalytic action of the nickel-phosphorus alloy layer formed previously on the surface of the substrate in response to the thermal decomposition reaction of acetylene gas.
  • the nickel-phosphorus alloy layer formed on the surface of a substrate in accordance with the present invention can be chemically plated in a simple manner on an optional substrate, irrespective of conductive and non-conductive materials, according to plating technique known as the electroless plating method without necessitating a direct current power source as may be seen in the case of common plating procedure.
  • plating technique known as the electroless plating method without necessitating a direct current power source as may be seen in the case of common plating procedure.
  • the nickel-phosphorus alloy layer of the present inven tion satisfies the requirements as catalyst and is sufficiently of commercial value.
  • nickel in which a solid solution of phosphorus is supersaturated coexists with a compound of nickel with phosphorus and, they have such properties that they eventually form, when heated, crystalline nickel and a nickel-phosphorus compound of Ni,-,P.
  • amorphous nickel and a nickelphosphorus compound of Ni,P in which .v is about 2 play individually the most effective role as catalyst.
  • any nickel-phosphorous alloys can display their efficiency as catalyst in practicing the process of the present invention so long as the amount of the total phosphorus component is 4% by weight or more.
  • this alloy is converted on heating into crystalline nickel and the compound of NiHP, whereby catalytic action of said alloy for formation of graphite due to thermal decomposition of acetylene gas is markedly reduced and finally its catalytic action completely disappears. Therefore, in case a hydrocarbon gas is subjected to thermal decomposition, it is necessary to employ such heating temperature or rate of temperature elevation as may not lose a catalytic action of the nickel-phosphorus alloy layer.
  • a process for forming a carbon coating on the surface of a substrate characterized by comprising the steps of plating the surface of said substrate with a nickel-phosphorus alloy containing 4-l2 percent by weight of phosphorus to form thereon a nickel-phosphorous alloy layer, and of heating the nickel-phosphorus alloy layer-coated substrate in a non-combustible reaction gas composed mainly of at least one of such inert gases as nitrogen, helium and argon and admixed with 0.1-1.5 percent by volume of acetylene gas at a temperature of 450700C and at a rate of temperature elevation so that a catalyst ability of said nickel-phosphorus alloy layer in formation of carbon from said acetylene gas.
  • a non-combustible reaction gas composed mainly of at least one of such inert gases as nitrogen, helium and argon and admixed with 0.1-1.5 percent by volume of acetylene gas at a temperature of 450700C and at a rate of temperature elevation so that
  • a process according to the embodiment mentioned above which process is characterized by using the reaction gas composed mainly of at least one of such inert gases as nitrogen, helium, and argon and containing 0.1-1.5 percent by volume of acetylene gas and, in addition thereto, at least one member selected from 0.1 percent by volume or more of LPG. and 0.1 percent by volume or more of methane gas in an amount within such a range that the resulting whole mixed gas may become non-combustible.
  • the reaction gas composed mainly of at least one of such inert gases as nitrogen, helium, and argon and containing 0.1-1.5 percent by volume of acetylene gas and, in addition thereto, at least one member selected from 0.1 percent by volume or more of LPG. and 0.1 percent by volume or more of methane gas in an amount within such a range that the resulting whole mixed gas may become non-combustible.
  • the following procedure may be applicable to the preparation of a plating solution from which is provided a nickel-phosphorus alloy plated layer to be utilized as a catalyst material in the reaction of a carboncontaining gas in accordance with the process of the present invention.
  • SUMER a trade name of a product of Nihon Kanizen K.K.
  • hydrochloric acid or aqueous ammonia is added so that a pH value of the mixture may be maintained within the range from 4-l0.
  • a substrate having a thickness of 0.] mm
  • carbon coating treatment for example, an iron sheet
  • the substrate is then immersed on the said plating solution to effect plating while maintaining the temperature of said plating solution at C according to the electroless plating method, whereby a nickel-phosphorus alloy plated layer is obtained.
  • the phosphorus content in said layer being different according to the pH value of said plating solution.
  • FIG. 1 is a graph showing the relationship between a pH value of a plating solution and an amount of phosphorus contained in the resulting alloy plated layer.
  • FIG. 2 is a sketch showing an example of the manufacturing apparatus illustrating a process for preparing a carbon coating.
  • substrates 1 plated with a nickel-phosphorus alloy in the manner mentioned above are inserted into reaction tube 3 into which is introduced reaction gas 2 comprising a mixture containing, for example, l.0 percent by volume of acetylene gas, 10% by volume of methane gas, 05 percent by volume of a gas obtained by vaporizing L.P.G. and nitro gen gas as the remainder (88.5 percent by volume).
  • reaction gas 2 comprising a mixture containing, for example, l.0 percent by volume of acetylene gas, 10% by volume of methane gas, 05 percent by volume of a gas obtained by vaporizing L.P.G. and nitro gen gas as the remainder (88.5 percent by volume).
  • the temperature inside reaction furnace 4 is previously fixed at an optional temperature within the range from 450 to 700C, and the amount of said reaction gas 2 is previously and sufficiently controlled so that a predetermined amount thereof may accurately
  • the nickel-phosphorus alloy plated substrate is heated in a very short time such as 0.5 to 1 minute up to a suitable heating temperature within the said range from 450 to 700C, and the heating of said substrate is effected in an atmosphere of said reaction gas 2 for a predetermined time. After completion of the heating, the said substrates l are withdrawin from the said reaction tube 3 through one end 5 of the tube.
  • FIG. 3 shows an amount of carbon deposited (curve A), according to the treatment methods explained above, on the surface of a substrate and'a porosity (curve B) of said carbon deposited. It is shown from this figure that both the amount of carbon deposited and the porosity thereof change according to the amount of phosphorus contained in the nickelphosphorus alloy layer formed on the substrate. Generally, it is seen that the more is increased the amount of phosphorus contained in the alloy layer, the more are increased both the amount of carbon deposited and the porosity thereof.
  • the relationship between the rate of deposition of carbon and the composition of the nickelphosphorus alloy plated layer does not change so much correlatively even when the absolute value of the rate of reaction changes according to change in composition or reaction temperature of the reaction gas.
  • the catalytic action of the nickelphosphorus alloy layer exerts a great influence on the carbon-depositing reaction at a low temperature of 450-700C.
  • the catalytic action of the nickelphosphorus alloy layer is closely related to the existence of a nickel-phosphorus compound, Ni P, which is separated at the very early stage of reaction from the nickel-phosphorus alloy plated layer. The higher is the content of phosphorus, the more is the amount of Ni l separated and the larger is the catalytic ability of the alloy layer. From this, it follows that the amount of carbon deposited is increased.
  • the porosity of the deposited carbon coating tends to excessively increase, as is clear from the porosity of carbon deposited (curve B shown in FIG. 3).
  • the porosity of the carbon deposited becomes 35 percent or more, with the result that the strength of the carbon film obtained thereby is markedly reduced.
  • the upper limit of the phosphorus content in the nickel-phosphorus alloy plated layer is preferably 12 percent by weight.
  • the phosphorus content becomes less than 4 percent, the amount of carbon deposited thereby is extremely small and, moreover, the thickness of the carbon coating obtained is uneven.
  • the phosphorus content in the nickel-phosphorus alloy plated layer is preferably within the range from 4 to 12 percent by weight for the purpose of obtaining a dense and stiff carbon film.
  • the thickness of nickel-phosphorus alloy plated layer provided on the surface of a substrate does not affect so much the amount of carbon deposited and others. This is because the reaction is carried out at a relatively low temperature such as 450700C. and hence the alloy layer is heated from room temperature up to the reaction temperature in a relatively short time, whereby the alloy reacts with the carboncontaining gas prior to the alloy layer diffuses into the substrate, and then acts to deposit a very slight amount of carbon particles which become henceforth nuclei for carbon to be deposited. That is, the nickel-phosphorus alloy plated layer acts as catalyst for the deposition of carbon even when the thickness of the layer is extremely thin.
  • the thickness of the nickel-phosphorus alloy plated layer on the substrate is preferably about 0.1 micron or thicker, whereby the presence of the alloy layer on the substrate can be confirmed at least by the visual inspection and the subsequent operational steps can be stably assured. Even if the plated layer is thick, no substantial adverse effect on the carbon deposition operation is seen. Since the nickel-phosphorus alloy plating solution is relatively expensive, the use of an unnecessarily thick layer increases the cost of production and is not economically advantageous. Taking all these considerations into account together with other factors, the thickness of the nickel-phosphorus alloy plated layer is advantageously about 6 microns or thinner. The alloy layer having an unnecessarily large thickness is undesirable. because such thick layer sometimes peels ofi' from the substrate during the carbon-deposition step.
  • the nickel-phosphorus alloy plated layer plays a very important role in the deposition of carbon at a low temperature and it is also a fact that the properties of said layer exert great influence upon the deposition of carbon.
  • the following experiment was conducted. Specimens were obtained by plating iron sheet substrates with nickel-phosphorus containing 8 percent by weight of phosphorus to form thereon a nickelphosphorus alloy layer having a thickness of l micron. The specimens were subjected to heat treatment in pure nitrogen gas stream for a predetermined time at the heating temperatures of 400C, 500C and 600C, respectively.
  • curves C, D and E show the cases where the heating temperatures of the nickelphosphorus alloy plated substrates in the nitrogen gas stream were 400C, 500C and 600C, respectively.
  • the longer is the heat treatment time in the nitrogen gas stream the smaller is the amount of carbon deposited.
  • this figure shows that when the heat treatment temperature of the alloy layer is higher, the amount of carbon deposited by decomposition is sharply decreased by heating for an extremely short time. It has been understood that when heat is applied in the manner as described above to the nickel-phosphorus alloy plated layer prior to the deposition of carbon, the catalytic ability of said layer is reduced.
  • Such phenomenon is considered ascribable to the fact that the catalytic ability of the said layer is reduced due to conversion attended by heating of the compound Ni- ,P in the said layer into Ni P and other compounds, and to extinction attended by heating of various defects in the lattice which have been introduced into said layer (the nickel-phosphorus alloy plated layer obtained by the method as explained previously is well known to be in a non-crystalline state). Accordingly, in the case of the present invention where a nickel-phosphorus alloy plated layer is utilized as a catalyst, heat treatment of said layer prior to deposition of carbon to form a carbon coating should be avoided as much as possible. From this, it follows that the rate of temperature elevation up to the reaction temperature, i.e. 450-700C, be efiected as quickly as possible.
  • l5 percent by volume of acetylene gas is introduced at a rate of l I per minute into a reaction tube having an inside diameter of 35 mm to deposit carbon by reaction of acetylene gas under heating to coat an iron sheet substrate of 23 mm in length. 23 mm in width and 0.1 mm in thickness plated with a nickel-phosphorus alloy containing 8 percent by weight of phosphorus.
  • the reaction temperature. temperature elevation time. and reaction time are 540C, less than 30 seconds. and 20 minutes. respectively.
  • the addition ofa small amount of L.P.G. has a great effect on the amount of carbon deposited. and it is understood that a sufficiently satisfactory carbon coating can be obtained by the addition of L.P.G.
  • FIG. 5 shows the results of an experiment where commercially available L.P.G. is used.
  • This L.P.G. contains about 60 to about percent by volume of propane gas, and the remainder thereof contains butane gases and impure gases such as propylene. butadiene, butene and others. These contaminant gases. however. do not act disfavorably on the deposition of carbon by the reaction of the reaction gas of nitrogen acetylene L.P.G. system. but serve to bring about good results as a whole.
  • the upper limit of the amount of L.P.G. to be added should be limited to such a range that the starting mixed gas may remain incombustible even when brought into contact with any amount of air. Such range is 7-15 percent by volume, though it varies depending on the concentration of acetylene in the starting mixed gas.
  • FIG. 6 shows change in the amount of carbon deposited when the proportion of acetylene gas in the nitrogen L.P.G. (0.5 percent by volume) mixed gas.
  • the reaction (heating) temperature is 560C
  • the temperature elevation time and the reaction (heating) time are less than 30 seconds and 20 minutes, respectively
  • the flow rate of the gas is 6 liters per minute, and other conditions are the same as shown in the embodiment illustrated by FIG. 5.
  • the amount of acetylene is more than 1.5 percent by volume.
  • the resulting carbon coating becomes somewhat porous.
  • the upper limit of the amount of acetylene gas to be mixed with a carrier gas is preferably L5 percent by volume.
  • at least 0.] percent by volume of acetylene gas should be mixed with the carrier gas.
  • the present invention has such advantages, as compared with the conventional reduced pressure method in which the deposition of carbon is effected in an atmosphere under reduced pressure, that because of the practice of the deposition of carbon under atmospheric pressure the apparatus used therefor is very simple, the size of the object to be treated is not restricted, and the desired car bon coating can be obtained on a large scale with low cost.
  • any materials can be used so long as the materials as substrates can be plated with the present nickelphosphorus alloy because the deposition of carbon can be achieved due mainly to the properties of said alloy used, and as long as said materials as substrates can resist to heating at a temperature of about 450 to about 700C. This is also one of the characteristic features of the present invention.
  • a process for forming carbon coatings which process is characterized by comprising a step of heating a nickel-phosphorus alloy-plated substrate in an atmosphere of a reaction gas comprising acetylene gas, said atmosphere being reduced in pressure to Torr or less, at a temperature of about 500 to about 700C and at such a rate of the temperature elevation that the nickel-phosphorus plated layer may not lose its catalytic ability for deposition of carbon.
  • a process for forming carbon coatings which process is characterized by using in the above-mentioned process a reaction gas containing acetylene gas and at least one of hydrogen and methane gas.
  • FIG. 7 shows the results of the formation of carbon coatings on substrates, wherein specimens of iron sheets of 0. l 8 mm in thickness were coated with a nickel-phosphorus alloy containing 8 percent by weight of phosphorus by use of SUMER plating solution adjusted pH to 6.0 to form thereon an alloy layer of l micron in thickness, the specimens were then individually heated at a temperature of about 600C in vacuo of 10 Torr for 5 minutes, 10 minutes, and 20 minutes, respectively, and thereafter acetylene gas of a pressure of about l0 Torr was introduced to bring about thermal decomposition reaction.
  • FIG. 7 shows the results of the formation of carbon coatings on substrates, wherein specimens of iron sheets of 0. l 8 mm in thickness were coated with a nickel-phosphorus alloy containing 8 percent by weight of phosphorus by use of SUMER plating solution adjusted pH to 6.0 to form thereon an alloy layer of l micron in thickness, the specimens were then individually heated at a temperature of about 600C in vacuo of 10 Tor
  • FIG. 8 shows the results of the investigation on the efficiency as catalyst of the nickel-phosphorus alloy plated having a thickness of about 0.6 microns layers formed on substrates, wherein each substrate was intro Jerusalem into an atmosphere of acetylene gas having a pressure of 10 Torr heated at 600C to effect reaction and thereby to check the relationship between the par tial pressure of hydrogen formed by thermal decomposition of acetylene gas and the reaction time.
  • curve A indicates the partial pressure of hydrogen of one of the specimens as measured by previously subjecting said specimen to preliminary heating in vacuo at about 600C for 30 minutes. thereby rendering the specimen inactive as a catalyst.
  • curve B shows the partial pressure of hydrogen of the other specimen as measured in its state as plated without subjecting to the said preliminary heating.
  • the temperature of the specimens during the reaction time is represented by curve C.
  • the reaction begins to take place when the heating temperature has reached about 500C. the thermal decomposition proceeds rapidly for the first 10 minutes of the reaction time and, thereafter a mild reaction continues for 30 minutes or more. i.e. even after extinction of said catalytic action.
  • evolution of hydrogen is not observed at all. As a natural consequence, no deposition of carbon is observed at all.
  • the above facts shows not only the catalyst plays at the initial stage of deposition of carbon :1 very important role but also mean that when the deposition of carbon has once started, the carbon successively deposits even after the catalytic action has disappeared.
  • the thickness of the nickel-phosphorus alloy plated layer is sufficiently 0.1 micron or thicker.
  • the initial deposition of carbon by the catalytic action as mentioned above is very important. if the time required to elevate the temperature of 400C up to the temperature at which the thermal decomposition of acetylene gas begins to start excessively long, a dense carbon coating can be obtained no longerv This critical time is called a critical heating time.
  • the critical heating time at varying heating temperatures starting from 400C were investigated to obtain the results as shown in the following table.
  • FIG. 9 shows the relationship between the heating time and the amount of carbon deposited (mg/cm which is obtained by subjecting each of specimens prepared by plating according to the electroless plating method iron sheet of 20 mm in length. 20 mm in width and 0.2 mm in thickness with a nickel-phosphorus alloy to reaction in a furnace heated at the temperature range from 550 to 640C in three kinds of acetylene gas for about 30 minutes.
  • C H having a pressure of 10 Torr in the case of curve D.
  • the decomposition reaction of methane gas is an endothermic reaction.
  • the heating temperature is below about 600C
  • a rapid deposition of carbon from acetylene gas due to the action of the catalyst has been suppressed.
  • the means for suppressing the rapid deposition of carbon resulted from the thermal decomposition of acetylene gas under the action of the catalyst it is preferable, including a method in which the amount of acetylene is reduced and the reaction is effected under reduced pressure. in addition to the above-mentioned means, that the temperature of below about 700C is selected as the heating temperature. At a temperature above about 700C.
  • the reaction is undesirably effected because there are brought about not only an undesirable effect of the heating temperature on the substrate but also decomposition of methane gas in the case the mixed reaction contains methane gas. whereby other factors arise. which factors should also be taken into consideration.
  • a process for forming a carbon coating on the surface ofa substrate characterized by comprising a step of plating the surface of the substrate with a nickel-phosphorus alloy to form thereon a nickel-phosphorus alloy layer containing at least 5 percent of phosphorus, a step of oxidizing said nickelphosphorus alloy layer, and a step of heating the substrate having thereon the oxidized nickel-phosphorus alloy layer at a temperature of 500 to 650C in a nonoxidative reaction gas containing 0.0 l 5 to 5 percent by volume of acetylene gas.
  • formation on a substrate of a desired carbon coating can be accomplished by the following four procedures.
  • the first one is to limit the heating temperature of the substrate, such as an iron sheet, employed at the time of coating step to a relatively low temperature of below about 650C
  • the second one is to previously provide a nickel-phosphorus alloy layer on the surface of the substrate.
  • the third one is to carry out a preliminary oxidation treatment of said nickelphosphorus alloy layer prior to a coating treatment with thermally decomposed carbon
  • the fourth one is to the optimum composition of a mixed gas from which the carbon is deposited by reaction under heat- Referring first to FIG.
  • FIG. l1 shows the influence on the amount of carbon deposited of the concentration of oxygen in the nitrogen gas stream as an atmosphere gas when the aforesaid nickel-phosphorus alloy layer has been subjected to the aforesaid preliminary oxidation treatment, provided that the content of phosphorus in the aforesaid nickel-phosphorus alloy layer was 8 percent by weight.
  • the treatment subsequent to the preliminary oxidation treatment was carried out in the manner similar to that in the case of FIG. 10, i.e. the subsequent carbon coating treatment was effected in a reaction gas containing about 0.05 percent by volume of acetylene at about 600C for 20 minutes.
  • the present preliminary oxidation treatment is not limited to such treatment conditions as illustrated above.
  • a preliminary oxidation of the nickel-phosphorus alloy layer in air of about 0.] Torr at about 600C for 10 minutes leads to formation of a favorable carbon coating.
  • the heating temperature in the preliminary oxidation treatment is not limited to 600C. Any conditions under which the oxidation of the said alloy layer is effected to a slight extent may be preferably employed for obtaining favorable carbon coatings in a manner as illustrated in the aforesaid case.
  • the effect of the preliminary oxidation treatment ofthe alloy layer is that by virtue of such oxidation treatment. the catalytic ability of said alloy layer is revived.
  • the present invention is illustrated below with reference to examples. All the nickel-phosphorus alloy layers used in these examples were formed according to the electroless plating method using a commercially available plating solution known as a trade name. SU- MER.” ln Examples 1-4, all the alloy layers used contain 8 percent by weight of phosphorus. The preliminary oxidation treatment was carried out in each case in a nitrogen atmosphere comprising 0.005 percent by volume of oxygen at a temperature of about 600C for l0 minutes.
  • EXAMPLE l An iron sheet substrate of 0.15 mm in thickness plated on its one surface with nickel-phosphorus alloy to form thereon a nickel-phosphorus alloy layer of about 1 micron in thickness was subjected to a preliminary oxidation. The substrate was then heated at a temperature of 560C for 20 minutes in the presence of a reaction gas stream comprising nitrogen gas containing 0.05 percent by volume based on the nitrogen gas of acetylene gas. thereby allowing carbon contained in said reaction gas to deposit on the surface of said nick' el-phosphorus alloy layer coated substrate to form a carbon coating thereon. The thus obtained carbon coating was found to be extremely dense and have an amount of carbon deposited of l mg/cm and a carbon density of 1.94 g/cm.
  • EXAMPLE 2 An iron sheet substrate of 0.15 mm in thickness plated on its one surface with nickel-phosphorus alloy to form thereon a nickel-phosphorus alloy layer was subjected to a preliminary oxidation treatment. The substrate was then heated at a temperature of 560C for 20 minutes in the presence of a reaction gas stream comprising methane gas containing 0.5 percent by volume based on the methane gas of acetylene gas. thereby allowing carbon contained in said reaction gas to deposit on the surface of the nickel-phosphorus alloy layer-coated substrate to form a carbon coating thereon. The carbon coating thus obtained was found to be extremely dense and have an amount of carbon deposited of 1.2 mg/cm and a carbon density of 2.20 g/cm.
  • the concentration of acetylene gas contained in the methane gas may be increased upmost to 5 percent by volume. In that case. however. a density of carbon in the resulting carbon coating tends to decrease to a some extent.
  • EXAMPLE 3 An iron sheet substrate of 0.15 mm in thickness plated on its one surface with nickel-phosphorus alloy to form thereon a nickel-phosphorus alloy layer was subjected to a preliminary oxidation treatment. The substrate was then heated at a temperature of about 560C for 20 minutes in the presence of a reaction gas stream comprising a gas obtained by vaporizing L.P.G.. said gas containing 0.7 percent by volume based on L.P.G. of acetylene gas. thereby allowing carbon contained in said reaction gas to deposit on the surface of the nickel-phosphorus alloy layer coated-substrate to form a carbon coating thereon.
  • a reaction gas stream comprising a gas obtained by vaporizing L.P.G.. said gas containing 0.7 percent by volume based on L.P.G. of acetylene gas.
  • the carbon coating thus obtained was found to be relatively thick in its thickness and dense, and have an amount of carbon deposited of about 2.5 mg/cm and a carbon density of 2.18 g/cm? in this example, the concentration of acetylene contained in L.P.G. may be increased upmost to 5 percent by volume. In that case. however. a density of carbon in the resulting carbon coating tends to decrease to some extent.
  • EXAMPLE 4 An iron sheet substrate of 0. l 5 mm in thickness plated on its one surface with nickel-phosphorus alloy to form thereon a nickelphosphorus alloy layer of about 1 micron in thickness was subjected to a preliminary oxidation treatment. The substrate was then heated at a temperature of about 560C for minutes in the presence of a reaction gas stream comprising a mixture of0.2 percent acetylene gas, 1 percent L.P.G.. 4 percent methane gas and 94.8 percent nitrogen gas in terms of percent by volume based on the mixture, thereby allowing carbon contained in said reaction gas to deposit on the surface of the nickel-phosphorus alloy layer-coated substrate to form a carbon coating thereon. The carbon coating thus obtained was found to be dense and have an amount of carbon deposited of about l8 mg/cm' and a carbon density of 1.96 g/cm.
  • reaction gas used in this example was noncombustible. it has been found quite effective to use said reaction gas in promoting a safe operation.
  • reaction gas having any composition, from which the carbon contained therein is allowed to deposit. so long as said reaction gas contains 0.0l-5 percent by volume based on the reaction gas of acetylene gas and is of a non oxidative composition free from such an oxidative gas as oxygen. ln that case. the reaction gas may be mixed suitably with such combustible gas as LPG. or methane gas. however. it is preferably from the standpoint of handling to use a reaction gas comprising a mixture of such an inert gas as nitrogen or argon and such a combustible gas as L.P.G. and/or methane gas in an amount within such a range that the resulting whole mixed gas may become non-combustible.
  • the process of the present invention it is possible to coat the surface of a very thin iron sheet substrate having a thickness of 0.15 mm with dense carbon in any given thickness with unerring precision and in a simple and safe manner. while it was almost impossible in the prior art processes to practice such coating as in the present invention.
  • the process of the present invention moreover. has such characteristic that since the temperature necessary for effecting a carbon-depositing reaction in the present process is low as compared with that used in the prior art processes, various disadvantages which may be associated with a high temperature heating employed in the prior art processes can be effectively avoided.
  • the process of the present invention is extremely effective as a process, in particular. for coating with carbon a shadow mask for color picture tube of television and leads to excellent results in an improvement in technique for the production of the shadow mask.
  • EXAMPLE 5 A 0.15 mm thick iron sheet shadow mask for color picture tube of television was washed with hydrochloric acid to remove completely from the surface thereof the oxide formed thereon. The mask thus washed as such was immersed for about 2 minutes in SUMER electroless nickel plating bath (temperature of the bath had been controlled to be maintained at C). a pH value of which had been previously adjusted to 6.0. In this case. special consideration was given so that the plating bath was thoroughly stirred so as to extend sufficiently uniformly over the circumferences ofa large number of small pores provided on the shadow mask. thereby uniformly plating every portion of the shadow mask with a nickel-phosphorus alloy in thickness of about 0.30.5 micron. After completion of the plating treatment.
  • the shadow mask was pulled out from the plating bath and washed thoroughly with pure water and thereafter dried quickly. Subsequently. the inside of a heating furnace was once evacuated until a pressure of l X 10" to l X 10 Torr was attained, said heating furnace being constructed by use of such material. for example. as quartz which may not deposit carbon by reaction with acetylene at about 600C. Therafter. acetylene was introduced into the heating furnace so that the degree of vacuum indicated by Pirani indicator provided in the said furnace may reach 5 Torr. Into the furnace, the inside temperature of which had been heated to about 600C. was then placed the shadow mask while giving sufficient consideration not to destruct the above-mentioned inside atmosphere of the furnace (in this case.
  • the shadow mask had not been preheated).
  • the reaction was carried out at that temperature for about 30 minutes. thereby forming on the surface of said shadow mask a carbon coating having an amount of carbon deposited of about l mg/cm and a thickness of about 4.5 micronsv Thereafter the carbon-coated shadow mask was conveyed to a cooling chamber and then taken out of the chamber. Microscopic observation of the thus obtained carbon coating under magnification of about 600 times showed in some cases that small spheres of carbon in the form of a ball of waste thread were present on the surface of the carbon coat ing. lf such carbon spheres are actually present on the surface of the carbon coating formed on a shadow mask.
  • a substrate on the surface of which a carbon coating is to be provided, with a nickel-phosphorus alloy to form thereon a layer thereof, to deposit from acetylene on the surface of the nickel-phosphorus alloy layercoated substrate by thermal decomposition reaction of the acetylene gas at relatively low temperatures utilizing catalytic action of the said nickel-phosphorus alloy layer, and to suppress or control the thermal decomposition reaction of the acetylene gas by adjusting the composition of the reaction gas containing the acetylene gas, thereby forming a dense and uniformly thick carbon coating on the surface of the substrate in a simple manner with high operational stability.
  • the present invention therefore, greatly contributes to advancement and improvement in the industrial technology concerned and also brings about large economical advantages.
  • a process for forming a carbon coating on an iron surface of an article to be coated which process comprises the steps of first forming on the iron surface of said article a nickel-phosphorus alloy layer having an amount of 4 12 percent by weight of phosphorus, and of then heating the nickel-phosphorus alloy layercoated article in a non-combustible gas mixture containing a thermally decomposable hydrocarbon gas, thereby effecting a thermal decomposition reaction of said gas at a temperature below 700C to deposit carbon contained in said gas on the surface of said nickelphosphorus alloy layer-coated article to form the carbon coating thereon, said nickel-phosphorus alloy layer effecting catalytic action to deposit carbon with a nickel-phosphorus compound of said alloy layer, so that said carbon coating is firmly bonded to said surface at said temperature.
  • noncombustible gas contains an inert gas selected from the group consisting of nitrogen, helium, and argon.
  • noncombustible gas also contains Liquefied Petroleum Gas or methane gas.
  • noncombustible gas is composed mainly of an inert gas selected from the group consisting of nitrogen, helium,
  • said noncombustible gas containing at least one member selected from the group consisting of 0.1 1.5% by volume of acetylene gas, 0.1% or more of Liquefied Petroleum Gas, and 0.l percent or more of methane gas in an amount within such a range that the resulting whole mixed gas is non-combustible.
  • non-combustible gas contains further at least one member selected from the group consisting of ethane and ethylene gases in an amount within such a range that the resulting whole mixed gas is non-combustible.
  • noncombustible gas comprises acetylene gas and at least one member selected from the group consisting of hydrogen and methane gases.
  • a process according to claim 15, wherein the article to be coated with carbon is a shadow mask for color picture tube of television.
  • non-combustible gas contains ().l to 1.5 percent by volume of acetylene gas.
  • noncombustible gas contains an inert gas selected from the group consisting of nitrogen, helium, and argen.
  • non-combustible gas is composed mainly of an inert gas selected from the group consisting of nitrogen, helium. and argon, said hydrocarbon-containing gas containing at least one member selected from the group consisting of 0. l 5l .5 percent by volume of acetylene gas, at least 0.1% by volume of Liquefied Petroleum Gas, and at least 0.1% by volume of methane gas in an amount within such a range that the resulting whole mixed gas is non-combustible.
  • an inert gas selected from the group consisting of nitrogen, helium. and argon
  • said hydrocarbon-containing gas containing at least one member selected from the group consisting of 0. l 5l .5 percent by volume of acetylene gas, at least 0.1% by volume of Liquefied Petroleum Gas, and at least 0.1% by volume of methane gas in an amount within such a range that the resulting whole mixed gas is non-combustible.
  • non-combustible gas contains further at least one member selected from the group consisting of ethane and ethylene gases in an amount within such a range that the resulting whole mixed gas is non-combustible.
  • a process according to claim 26, wherein the article to be coated with carbon is a shadow mask for color picture tube of television.
  • acetylene-containing gas comprises acetylene gas and at least one member selected from the group consisting of hydrogen and methane gases.
  • a process according to claim 32, wherein the reduced pressure is a pressure of 100 Torr or less.
  • an atmosphere of the non-combustible gas is an acetylenecontaining gas having a pressure of 100 Torr or less.
  • acetylene-containing gas comprises acetylene gas and at least one member selected from the group consisting of hydrogen and methane gases.
  • the nickel-phosphorus alloy layer has a thickness of at least 1 micron and the acetylene-containing gas comprises acetylene gas and at least one member selected from the group consisting of hydrogen and methane gases.
  • a process according to claim 37, wherein the article to be coated with carbon is a shadow mask for color picture tube of television.
  • the nickel-phosphorus alloy layer contains at least 5 percent by weight of phosphorus based on the nickel.
  • non-combustible gas contains ().Ol-5 percent by volume of acetylene gas.
  • non-combustible gas contains an inert gas selected from the group consisting of nitrogen, helium. and argon.
  • noncombustible gas is composed mainly of an inert gas selected from the group consisting of nitrogen, helium, and argon, said non-combustible gas containing at least one member selected from the group consisting of 0.0l-S percent by volume of acetylene gas, at least 0.] percent by volume of Liquefied Petroleum Gas, and at least 0.1 percent by volume of methane gas in an amount within such a range that the resulting whole mixed gas is non-combustible.
  • an inert gas selected from the group consisting of nitrogen, helium, and argon
  • said non-combustible gas containing at least one member selected from the group consisting of 0.0l-S percent by volume of acetylene gas, at least 0.] percent by volume of Liquefied Petroleum Gas, and at least 0.1 percent by volume of methane gas in an amount within such a range that the resulting whole mixed gas is non-combustible.
  • a process according to claim 37 wherein the nickel-phosphorus alloy layer contains at least 5 percent by weight of phosphorus based on the nickel, and the non-combustible gas contains 0.(ll--S percent by volume of acetylene gas.
  • non-combustible gas contains an inert gas selected from the groups consisting of nitrogen, helium, and argon.
  • non-combustible gas is composed mainly of an inert gas selected from the group consisting of nitrogen. helium, and argon. and containing at least one member selected from the group consisting of Liquefied Petroleum Gas and methane gas in an amount within such a range that the resulting whole mixed gas is non-combustible.
  • a process for forming a carbon coating a surface comprising coating a carbon layer on a surface comprising a substrate of iron coated with a nickel-phosphorus alloy layer containing 4 l2 percent by weight of phosphorus by heating a non-combustible hydrocarbon containing gas at a temperature below 700C to thermally decompose said gas, thereby depositing carbon on said surface.
  • said nickel-phosphorus alloy layer effecting catalytic action to deposit carbon with a nickel-phosphorus compound of said alloy layer, so that carbon is firmly bonded to said surface at said temperature.
  • non-combustible gas contains 0.l-l.5 percent by volume of acetylene gas.
  • non-combustible gas contains an inert gas selected from the group consisting of nitrogen, helium. and argonr 63.
  • the non-combustible gas is composed mainly of an inert gas being at least one of nitrogen, helium, and argon, said non-combustible gas containing at least one of 0.1 -1.5 percent by volume of acetylene gas, 0.1% or more of Liquefied Petroleum Gas, and 0.1percent or more of methane gas in an amount within such a range that the resulting whole mixed gas is non-combustible.
  • non-combustible gas contains further at least one of ethane and ethylene gases in an amount within such a range that the resulting whole mixed gas is noncombustible.
  • non-combustible gas comprises acetylene gas and at least one of hydrogen and methane gases.
  • a process according to claim 59 further comprising the step of oxidizing said nickel-phosphorus alloy layer prior to said deposition of carbon on said surface.
US358647A 1972-05-12 1973-05-09 Process for forming carbon coatings Expired - Lifetime US3892890A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP47046396A JPS5143038B2 (de) 1972-05-12 1972-05-12
JP47046395A JPS5129718B2 (de) 1972-05-12 1972-05-12
JP47046394A JPS5143037B2 (de) 1972-05-12 1972-05-12

Publications (1)

Publication Number Publication Date
US3892890A true US3892890A (en) 1975-07-01

Family

ID=27292593

Family Applications (1)

Application Number Title Priority Date Filing Date
US358647A Expired - Lifetime US3892890A (en) 1972-05-12 1973-05-09 Process for forming carbon coatings

Country Status (3)

Country Link
US (1) US3892890A (de)
DE (1) DE2323928A1 (de)
FR (1) FR2208992A1 (de)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1067210A2 (de) * 1996-09-06 2001-01-10 Sanyo Electric Co., Ltd. Verfahren zur Abscheidung eines harten Kohlenstoff-Filmes auf einem Substrat und Klinge für einen elektrischen Rasierer
WO2001023303A1 (de) * 1999-09-29 2001-04-05 Electrovac, Fabrikation Elektrotechnischer Spezialartikel Gesellschaft M.B.H. Verfahren zur herstellung einer nanotube-schicht auf einem substrat
US6373177B1 (en) * 1997-12-01 2002-04-16 Samsung Display Devices Co., Ltd. Shadow mask for cathode ray tube and method of manufacturing same
WO2002075018A1 (de) * 2001-03-16 2002-09-26 Electrovac, Fabrikation Elektrotechnischer Spezialartikel Gesellschaft M.B.H. Ein ccvd-verfahren zur herstellung von röhrenförmigen kohlenstoff-nanofasern
US6574130B2 (en) 2001-07-25 2003-06-03 Nantero, Inc. Hybrid circuit having nanotube electromechanical memory
US6607614B1 (en) 1997-10-20 2003-08-19 Techmetals, Inc. Amorphous non-laminar phosphorous alloys
US6643165B2 (en) 2001-07-25 2003-11-04 Nantero, Inc. Electromechanical memory having cell selection circuitry constructed with nanotube technology
US20040022944A1 (en) * 2002-08-01 2004-02-05 Wolfgang Lerche Method and device for blacking components
US6706402B2 (en) 2001-07-25 2004-03-16 Nantero, Inc. Nanotube films and articles
US6784028B2 (en) 2001-12-28 2004-08-31 Nantero, Inc. Methods of making electromechanical three-trace junction devices
US6835591B2 (en) 2001-07-25 2004-12-28 Nantero, Inc. Methods of nanotube films and articles
US6911682B2 (en) 2001-12-28 2005-06-28 Nantero, Inc. Electromechanical three-trace junction devices
US6919592B2 (en) 2001-07-25 2005-07-19 Nantero, Inc. Electromechanical memory array using nanotube ribbons and method for making same
US7176505B2 (en) 2001-12-28 2007-02-13 Nantero, Inc. Electromechanical three-trace junction devices
US7274078B2 (en) 2001-07-25 2007-09-25 Nantero, Inc. Devices having vertically-disposed nanofabric articles and methods of making the same
US7304357B2 (en) 2001-07-25 2007-12-04 Nantero, Inc. Devices having horizontally-disposed nanofabric articles and methods of making the same
US7335395B2 (en) 2002-04-23 2008-02-26 Nantero, Inc. Methods of using pre-formed nanotubes to make carbon nanotube films, layers, fabrics, ribbons, elements and articles
US7560136B2 (en) 2003-01-13 2009-07-14 Nantero, Inc. Methods of using thin metal layers to make carbon nanotube films, layers, fabrics, ribbons, elements and articles
US7566478B2 (en) 2001-07-25 2009-07-28 Nantero, Inc. Methods of making carbon nanotube films, layers, fabrics, ribbons, elements and articles
US20140093419A1 (en) * 2012-10-02 2014-04-03 Hon Hai Precision Industry Co., Ltd. Mold made of nickel-phosphorus alloy

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4863818A (en) * 1986-06-24 1989-09-05 Sharp Kabushiki Kaisha Graphite intercalation compound electrodes for rechargeable batteries and a method for the manufacture of the same
US5391407A (en) * 1994-03-18 1995-02-21 Southwest Research Institute Process for forming protective diamond-like carbon coatings on metallic surfaces
DE19947381B4 (de) * 1999-10-01 2011-06-22 METAPLAS IONON Oberflächenveredelungstechnik GmbH, 51427 Vorrichtung zur Wärmebehandlung von Werkstücken, insbesondere zum Gasnitrieren, Nitrocarburieren und Oxidieren

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1862138A (en) * 1928-05-03 1932-06-07 Westinghouse Electric & Mfg Co Carbonized electrode and method of producing same
US2289614A (en) * 1940-08-07 1942-07-14 Int Nickel Co Nickel clad ferrous article
US3077421A (en) * 1961-03-13 1963-02-12 Gen Am Transport Processes of producing tin-nickelphosphorus coatings
US3619262A (en) * 1970-01-16 1971-11-09 Exxon Research Engineering Co Process for depositing carbon on iron
US3791847A (en) * 1970-07-27 1974-02-12 Kureha Chemical Ind Co Ltd Process for the production of incombustible carbonaceous material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1862138A (en) * 1928-05-03 1932-06-07 Westinghouse Electric & Mfg Co Carbonized electrode and method of producing same
US2289614A (en) * 1940-08-07 1942-07-14 Int Nickel Co Nickel clad ferrous article
US3077421A (en) * 1961-03-13 1963-02-12 Gen Am Transport Processes of producing tin-nickelphosphorus coatings
US3619262A (en) * 1970-01-16 1971-11-09 Exxon Research Engineering Co Process for depositing carbon on iron
US3791847A (en) * 1970-07-27 1974-02-12 Kureha Chemical Ind Co Ltd Process for the production of incombustible carbonaceous material

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6572936B1 (en) 1996-06-09 2003-06-03 Sanyo Electric Co., Ltd. Hard carbon film-coated substrate and method for fabricating the same
EP1067210A3 (de) * 1996-09-06 2002-11-13 Sanyo Electric Co., Ltd. Verfahren zur Abscheidung eines harten Kohlenstoff-Filmes auf einem Substrat und Klinge für einen elektrischen Rasierer
EP1067210A2 (de) * 1996-09-06 2001-01-10 Sanyo Electric Co., Ltd. Verfahren zur Abscheidung eines harten Kohlenstoff-Filmes auf einem Substrat und Klinge für einen elektrischen Rasierer
US6607614B1 (en) 1997-10-20 2003-08-19 Techmetals, Inc. Amorphous non-laminar phosphorous alloys
US6373177B1 (en) * 1997-12-01 2002-04-16 Samsung Display Devices Co., Ltd. Shadow mask for cathode ray tube and method of manufacturing same
WO2001023303A1 (de) * 1999-09-29 2001-04-05 Electrovac, Fabrikation Elektrotechnischer Spezialartikel Gesellschaft M.B.H. Verfahren zur herstellung einer nanotube-schicht auf einem substrat
US20020102353A1 (en) * 1999-09-29 2002-08-01 Electrovac, Fabrikation Electrotechnischer Spezialartikel Gesellschaft M.B.H. Method of producing a nanotube layer on a substrate
US7033650B2 (en) 1999-09-29 2006-04-25 Electrovac, Fabrikation, Elektrotechnischer Spezialartikel, Gesellschaft Mbh Method of producing a nanotube layer on a substrate
US20040081758A1 (en) * 2001-03-16 2004-04-29 Klaus Mauthner Ccvd method for producing tubular carbon nanofibers
WO2002075018A1 (de) * 2001-03-16 2002-09-26 Electrovac, Fabrikation Elektrotechnischer Spezialartikel Gesellschaft M.B.H. Ein ccvd-verfahren zur herstellung von röhrenförmigen kohlenstoff-nanofasern
US7384668B2 (en) 2001-03-16 2008-06-10 Electrovac, Fabrikation Elektrotechnischer Spezialartikel Gesellschraft M.B.H. CCVD method for producing tubular carbon nanofibers
US7335528B2 (en) 2001-07-25 2008-02-26 Nantero, Inc. Methods of nanotube films and articles
US7566478B2 (en) 2001-07-25 2009-07-28 Nantero, Inc. Methods of making carbon nanotube films, layers, fabrics, ribbons, elements and articles
US8101976B2 (en) 2001-07-25 2012-01-24 Nantero Inc. Device selection circuitry constructed with nanotube ribbon technology
US6835591B2 (en) 2001-07-25 2004-12-28 Nantero, Inc. Methods of nanotube films and articles
US20050063210A1 (en) * 2001-07-25 2005-03-24 Nantero, Inc. Hybrid circuit having nanotube electromechanical memory
US7745810B2 (en) 2001-07-25 2010-06-29 Nantero, Inc. Nanotube films and articles
US6919592B2 (en) 2001-07-25 2005-07-19 Nantero, Inc. Electromechanical memory array using nanotube ribbons and method for making same
US6942921B2 (en) 2001-07-25 2005-09-13 Nantero, Inc. Nanotube films and articles
US6706402B2 (en) 2001-07-25 2004-03-16 Nantero, Inc. Nanotube films and articles
US6643165B2 (en) 2001-07-25 2003-11-04 Nantero, Inc. Electromechanical memory having cell selection circuitry constructed with nanotube technology
US7056758B2 (en) 2001-07-25 2006-06-06 Nantero, Inc. Electromechanical memory array using nanotube ribbons and method for making same
US7120047B2 (en) 2001-07-25 2006-10-10 Segal Brent M Device selection circuitry constructed with nanotube technology
US6574130B2 (en) 2001-07-25 2003-06-03 Nantero, Inc. Hybrid circuit having nanotube electromechanical memory
US7342818B2 (en) 2001-07-25 2008-03-11 Nantero, Inc. Hybrid circuit having nanotube electromechanical memory
US7264990B2 (en) 2001-07-25 2007-09-04 Nantero, Inc. Methods of nanotubes films and articles
US7274078B2 (en) 2001-07-25 2007-09-25 Nantero, Inc. Devices having vertically-disposed nanofabric articles and methods of making the same
US7298016B2 (en) 2001-07-25 2007-11-20 Nantero, Inc. Electromechanical memory array using nanotube ribbons and method for making same
US7304357B2 (en) 2001-07-25 2007-12-04 Nantero, Inc. Devices having horizontally-disposed nanofabric articles and methods of making the same
US6979590B2 (en) 2001-12-28 2005-12-27 Nantero, Inc. Methods of making electromechanical three-trace junction devices
US7176505B2 (en) 2001-12-28 2007-02-13 Nantero, Inc. Electromechanical three-trace junction devices
US7521736B2 (en) 2001-12-28 2009-04-21 Nantero, Inc. Electromechanical three-trace junction devices
US6911682B2 (en) 2001-12-28 2005-06-28 Nantero, Inc. Electromechanical three-trace junction devices
US7915066B2 (en) 2001-12-28 2011-03-29 Nantero, Inc. Methods of making electromechanical three-trace junction devices
US6784028B2 (en) 2001-12-28 2004-08-31 Nantero, Inc. Methods of making electromechanical three-trace junction devices
US7335395B2 (en) 2002-04-23 2008-02-26 Nantero, Inc. Methods of using pre-formed nanotubes to make carbon nanotube films, layers, fabrics, ribbons, elements and articles
US7160576B2 (en) * 2002-08-01 2007-01-09 Ipsen International Gmbh Method and device for blacking components
US20040022944A1 (en) * 2002-08-01 2004-02-05 Wolfgang Lerche Method and device for blacking components
US7560136B2 (en) 2003-01-13 2009-07-14 Nantero, Inc. Methods of using thin metal layers to make carbon nanotube films, layers, fabrics, ribbons, elements and articles
US20140093419A1 (en) * 2012-10-02 2014-04-03 Hon Hai Precision Industry Co., Ltd. Mold made of nickel-phosphorus alloy

Also Published As

Publication number Publication date
FR2208992A1 (de) 1974-06-28
DE2323928A1 (de) 1973-12-13

Similar Documents

Publication Publication Date Title
US3892890A (en) Process for forming carbon coatings
JP2999085B2 (ja) 炭素複合体電極材料およびその炭素複合体電極材料の製造方法
Dresselhaus et al. Synthesis of graphite fibers and filaments
US7070833B2 (en) Method for chemical vapor deposition of silicon on to substrates for use in corrosive and vacuum environments
US20110177349A1 (en) Process for the modification of substrate surfaces through the deposition of amorphous silicon layers followed by surface functionalization with organic molecules and functionalized structures
CA1168119A (en) Inhibition of carbon accumulation on metal surfaces
JPS61500561A (ja) メタンから蒸着によるカ−ボンフアイバ−の製法
WO1996015284A1 (en) Method of producing reactive element modified-aluminide diffusion coatings
CN109449308A (zh) 一种石墨烯隔绝挡膜及制备方法
US3967029A (en) Boron-carbon alloy tape
US3769084A (en) Method for forming carbon coating and composite article with a carbonaceous coating thereon
US3112215A (en) Preparation of catalytically active coatings
DE19937255A1 (de) Korrosionsbeständige PEM-Brennstoffzelle
US6333072B1 (en) Method of producing adherent metal oxide coatings on metallic surfaces
US2344906A (en) Carbonizing metals
US2886468A (en) Nickel plating process
US2873208A (en) Deposition of refractory metals and alloys thereof
US3200015A (en) Process for coating high temperature alloys
US455230A (en) Ludwig mond
JPS5934230B2 (ja) 金属の表面処理方法
US4778625A (en) Electroconductive polymer and process for preparation thereof
GB2078699A (en) Coating of metallic substrates
US2753283A (en) Method of making nickel-carbon alloy sleeves
Audisio Chemical Vapor Deposition of Tin on Iron or Carburized Iron
JPH062937B2 (ja) 表面被覆鋼材の製造方法