US20150307981A1 - Surface sulfurization of a metal body by flame spray pyrolysis - Google Patents

Surface sulfurization of a metal body by flame spray pyrolysis Download PDF

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US20150307981A1
US20150307981A1 US14/653,517 US201314653517A US2015307981A1 US 20150307981 A1 US20150307981 A1 US 20150307981A1 US 201314653517 A US201314653517 A US 201314653517A US 2015307981 A1 US2015307981 A1 US 2015307981A1
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Prior art keywords
metal
process according
sulfur
organic compound
flame
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Robert Nikolaus Grass
Milan Fedurco
Antonio Delfino
Jean Paul Meraldi
Wendelin Jan Stark
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Compagnie Generale des Etablissements Michelin SCA
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Michelin Recherche et Technique SA Switzerland
Compagnie Generale des Etablissements Michelin SCA
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Assigned to COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN reassignment COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MICHELIN RECHERCHE ET TECHNIQUE S.A.
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    • C23C4/124—
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/0666—Reinforcing cords for rubber or plastic articles the wires being characterised by an anti-corrosive or adhesion promoting coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
    • B60C2009/0014—Surface treatments of steel cords

Definitions

  • the present invention relates to processes for the surface treatment of metals, in particular of metal bodies, which can be used as reinforcers in metal/rubber composites intended in particular for the manufacture of articles made of rubber, such as tyres.
  • Composites of metal/rubber type in particular for tyres, are well known. They are generally composed of a matrix made of unsaturated rubber, generally diene rubber, which can be crosslinked with sulphur, comprising metal reinforcing elements (or “reinforcers”), such as wires or cords made of carbon steel.
  • these composites must, in a known way, satisfy a large number of sometimes contradictory technical criteria, such as uniformity, flexibility, endurance in bending and compression, tensile strength, wear resistance and corrosion resistance, and must maintain this performance at a very high level for as long as possible.
  • the conventional process for connecting the rubber compositions to carbon steel consists in coating the surface of the steel with brass (copper/zinc alloy), the bonding between the steel and the rubber matrix being provided by sulphurization of the brass (formation of zinc and copper sulphides) during the subsequent vulcanization (that is to say, three-dimensional crosslinking by sulphur) of the rubber matrix.
  • This sulphurization process is reflected in particular by the in situ formation of metal clusters at the surface of the brass known as “dendrites”, around which it is assumed that the rubber matrix will anchor (by mechanical and chemical anchoring) during the vulcanization.
  • organic salts or complexes of cobalt are generally incorporated in this rubber matrix as adhesion-promoting additives. It is known that cobalt actively participates not only in the process of vulcanization of the rubber but also in that of dendritization of the brass by being incorporated in the dendrites themselves (by formation of Cu—Zn—Co intermetallic sulphides), according to complex mechanisms of redox reactions resulting, it is assumed, in the corrosion of the brass, in the dissolution of the metal and its redeposition in the form of these metal sulphide dendrites (sulphur-comprising dendrites). Reference may be made for further details to the RCT ( Rubber Chemistry and Technology ) publication, Vol. 78, pp. 426-457, author W. Stephen Fulton, entitled “ Steel tire cord - rubber adhesion, including the contribution of cobalt ”).
  • manufacturers of metal/rubber composites are on the lookout for novel adhesive solutions in order to adhesively bond metal reinforcers to rubber compositions, while overcoming, at least in part, the abovementioned disadvantages.
  • the present invention relates to a process for the surface sulphurization of a body, the surface of which comprises a layer of metal, referred to as surface metal, capable of forming sulphides, characterized in that it comprises at least one stage of flame spray pyrolysis of a sulphur precursor which generates hydrogen sulphide in the flame.
  • the metal reinforcers treated with the process of the invention exhibit the major advantage of being able to be subsequently adhesively bonded directly, that is to say without adhesion primer or addition of metal salt (in particular cobalt salt), to matrices of unsaturated rubber such as natural rubber.
  • any interval of values denoted by the expression “between a and b” represents the range of values extending from more than a to less than b (that is to say, limits a and b excluded), whereas any interval of values denoted by the expression “from a to b” means the range of values extending from a up to b (that is to say, including the strict limits a and b).
  • the invention thus relates to a process for the surface sulphurization of a body, whether it is metallic or nonmetallic, at least the surface of which comprises, for all or part, a layer of metal referred to as surface metal, this surface metal (hereinafter denoted “M”) being capable of forming sulphides.
  • This surface treatment has the essential characteristic of comprising a stage of flame spray pyrolysis, abbreviated to “FSP”, of a sulphur-donating precursor which generates hydrogen sulphide in the flame.
  • FSP stage of flame spray pyrolysis
  • the gas (H 2 S) formed is propelled, sprayed by the flame towards the surface of the body being treated, hence the name assigned to this technology.
  • metal sulphides are thus formed.
  • the process of the invention is preferably employed for the purpose of subsequently adhesively bonding the body thus treated to an ethylenically unsaturated rubber, that is to say a vulcanizable (crosslinking with sulphur) rubber, such as a diene elastomer.
  • an ethylenically unsaturated rubber that is to say a vulcanizable (crosslinking with sulphur) rubber, such as a diene elastomer.
  • Flame spray pyrolysis is a method well known today which has been essentially developed for the synthesis of ultrafine powders of simple or mixed oxides of various metals (e.g., SiO 2 , Al 2 O 3 , B 2 O 3 , ZrO 2 , GeO 2 , WO 3 , Nb 2 O 5 , SnO 2 , MgO, ZnO, Ce x Zr (1-x) O 2 ), having controlled morphologies, and/or their deposition on various substrates, this being the case starting from a great variety of metal precursors, generally in the form of sprayable organic or inorganic liquids which are preferably non-flammable; the liquids sprayed into the flame, on being consumed, give off in particular metal oxide nanoparticles which are sprayed by the flame itself onto these various substrates.
  • various metals e.g., SiO 2 , Al 2 O 3 , B 2 O 3 , ZrO 2 , GeO 2 , WO 3 , Nb 2 O
  • Metal M sulphides are understood to mean, in a known way, compounds which can be denoted symbolically by M x S y (in this general expression, depending on the applicable stoichiometry and the nature of the metal, x and y, which are identical or different, are nonzero integers identical to or different from 1) or also can be denoted more simply as M x S (in this expression, y being conventionally equal to 1, x is then an integer or decimal number other than zero).
  • this definition also encompasses the cases where several different metals (M then representing M1, M2, M3, and the like) are present at the surface of the treated body, in the form of mixed sulphides (for example of the M1 x1 M2 x2 M3 x3 S y type) of these various metals.
  • the surface metal M by definition capable of forming sulphides, is chosen from the group consisting of aluminium (Al), silver (Ag), cobalt (Co), copper (Cu), tin (Sn), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), zinc (Zn) and the metal alloys (for example binary, ternary or quaternary) comprising at least one of these elements, these metal alloys consequently being themselves capable of forming sulphides.
  • the surface metal is chosen from the group consisting of cobalt, copper, tin, iron, molybdenum, nickel, zinc and the metal alloys comprising at least one of these elements.
  • the surface metal is chosen from the group consisting of copper, zinc and the alloys comprising at least one of these elements, that is to say alloys of Cu and/or Zn. Mention will in particular be made, as metal elements which can participate in the composition of such alloys, in addition to Cu and/or Zn, of those chosen from the group consisting of cobalt, tin, iron, molybdenum and nickel.
  • the surface metal is more particularly chosen from the group consisting of copper, zinc and brass (Cu/Zn alloy), thus by definition a metal capable of forming zinc sulphide (ZnS) or copper sulphides (Cu x S, x here being an integer or decimal number varying from 1.0 to 2.0).
  • the invention applies very particularly to brass, in particular in the applications where the body treated by the process of the invention is a metal reinforcer intended to adhere subsequently to an unsaturated rubber matrix, such as natural rubber, in order to form a metal/rubber composite, such as those normally encountered in articles made of rubber, such as tyres.
  • “Sulphur precursor” or “sulphur-donating precursor”, capable of generating hydrogen sulphide (H 2 S) during its combustion in the flame, is understood to mean, in the present patent application, the product which is sprayed into the flame, whatever the form or the presentation of this product.
  • It can be sulphur, a sulphur-comprising starting compound or else a more complex product, for example a composition or a solution, comprising sulphur in whatever form. It might be solid, for example in the form of a powder, sprayed and melted directly in the flame; it is preferably liquid at ambient temperature (20° C.). It can be organic or inorganic and monosulphide, disulphide or polysulphide.
  • a sulphur-comprising starting compound is used and if the latter is not organic as such, it can advantageously be dissolved or dispersed in an organic solvent (such as, for example, benzene, cyclohexane, styrene or toluene) or an organic liquid, so as to form a sulphur-donating precursor which can then be described as organic.
  • an organic solvent such as, for example, benzene, cyclohexane, styrene or toluene
  • this sulphur-comprising starting compound is not liquid (for example in the solid sulphur form), it can advantageously be dispersed in an organic solvent or another appropriate liquid so as to form a sulphur-donating precursor which can be described as liquid.
  • the sulphur precursor is preferably an organic compound more preferably comprising from 1 to 15 carbon atoms; it can be monosulphide, disulphide or polysulphide, in particular of the saturated or unsaturated aliphatic or cycloaliphatic type, or of the aromatic type. More preferably still, it is an organic compound which is liquid at ambient temperature, in particular of the non-flammable type.
  • the sulphur precursor is an organic compound devoid of a nitrogen atom; more preferably still, it is also devoid of an oxygen atom and very preferably the sulphur precursor is an organic compound devoid of a heteroatom other than sulphur.
  • the sulphur precursor is an organic compound consisting exclusively of carbon, sulphur and hydrogen atoms.
  • organic sulphur-donating precursor is chosen from the group consisting of the following compounds:
  • this organic sulphur-donating precursor is chosen from the group consisting of thiophene and its derivatives, aliphatic or aromatic organic disulphides, aliphatic or aromatic organic polysulphides, acyclic or cyclic thioethers, and the mixtures of such compounds.
  • the sulphur-donating precursor is thiophene or a thiophene derivative.
  • This sulphur-comprising organic compound, of formula C 4 H 4 S, which is volatile and nonflammable, has here the direct function of sulphur donor; it can also advantageously be used as organic solvent.
  • the FSP treatment can be carried out at any temperature, of course lower than the melting point of the metal M. It might be carried out at a temperature, in particular at a temperature close to ambient temperature (23° C.). However, in order to optimize the duration and the effectiveness of the treatment, the temperature of the surface metal, during the sulphurization, is preferably between 50° C. and 500° C., more preferably between 100° C. and 350° C.
  • FIG. 1 illustrates, highly diagrammatically, without observing a specific scale, the principle of the FSP (flame spray pyrolysis) process of the invention and also an example of a device ( 1 ) which can be used in the implementation of this process.
  • FSP flame spray pyrolysis
  • the principle of the method is to inject a sulphur-donating precursor (P) and then to comminute it in a flame using a propellant and oxidizing gas; the combustion of the precursor (P) in the flame (F) makes possible the formation of the targeted entity (in this case, in accordance with the invention, hydrogen sulphide H 2 S).
  • a sulphur-donating precursor (P) and then to comminute it in a flame using a propellant and oxidizing gas
  • the combustion of the precursor (P) in the flame (F) makes possible the formation of the targeted entity (in this case, in accordance with the invention, hydrogen sulphide H 2 S).
  • the device 1 of this example essentially comprises three respective feeds:
  • the flame (F) generated by the combustion gas ( 14 ) and the oxidizing gas ( 13 ) which constitutes the FSP reactor a thermal reactor at very high temperature since the temperature inside the flame (F), depending on the preferred operating conditions given above, is greater than 500° C., for example between 600° C. and 800° C.
  • the FSP sulphurization treatment is in this instance carried out in an atmosphere “depleted in oxygen” (“reducing flame” or “reducing atmosphere” conditions), that is to say with the minimum of oxygen necessary (the trend is towards incomplete combustion), without which there will be no formation of hydrogen sulphide (and of other gaseous reducing entities); preferably, the oxygen content of the combustion chamber (measured immediately at the chamber outlet) is less than 200 ppm, in particular within a range from 5 to 200 ppm, preferably less than 100 ppm, in particular within a range from 10 to 100 ppm.
  • the whole of the combustion chamber (in the examples which follow, a simple fitted-out closed glove box) is thus swept with a stream of inert gas, such as nitrogen.
  • the height of the main flame (F) is typically between 5 and 10 cm.
  • the flame is placed, as a function of the desired intensity of the treatment, at a variable distance from the surface ( 17 ) of the metal M to be treated, which distance a person skilled in the art can easily define as a function of the specific conditions for implementing the invention.
  • This distance, denoted “d” in FIG. 1 measured between the base of the flame (F) and the surface ( 17 ) of the metal M, is preferably between 50 and 250 mm, in particular between 60 and 180 mm.
  • metal sulphides M x S are created by erosion, without any external contribution of metal being necessary, in contrast to the FSP techniques of the prior art (synthesis of metal oxides) mentioned in the introduction to the present account.
  • the duration of the treatment is typically from a few seconds to a few minutes, preferably from a few seconds to a few tens of seconds, depending of the specific conditions for implementing the invention, according in particular to the nature of the metal M, according to whether the body treated is stationary or, on the contrary, is moving in front of the flame at a given rate which can, for example, vary from a few tens of cm/min to several tens of m/min.
  • the plants used might comprise a combination of several flames in line.
  • nongaseous entities such as, for example, particles of metal or of metal oxide, contributed by precursors other than the sulphur-donating precursor described above, will be sprayed, simultaneously or nonsimultaneously, at the surface of the metal M to be treated.
  • FIG. 2 represents, highly diagrammatically, the surface condition of the metal M once it has been treated by FSP as indicated above.
  • the surface ( 17 ) of the metal M has been provided with a multitude of metal sulphide M x S nanoparticles (in this case, Cu x S and ZnS in the case where M is brass) of nanometric size, generally agglomerated in the form of dendrites ( 18 ) themselves in nanometric size.
  • Nanoparticles are understood to mean, by definition, particles, the size (diameter or greater dimension in the case of anisometric particles) of which is greater than 1 nm (nanometre) and less than 1 ⁇ m (micrometre), in contrast in particular to particles referred to as microparticles, the size of which is equal to or greater than 1 ⁇ m.
  • nanoparticles described here can be provided in the individual isolated state; usually, they are provided in the form of agglomerates of such nanoparticles, also known as “dendrites”. Such agglomerates (clusters, packets) of nanoparticles are capable, in a known way, of deagglomerating to give these nanoparticles under the effect of an external force, for example under the action of mechanical work. “Nanoparticles” should thus be understood as meaning the indivisible assembly (i.e., which cannot be cut, divided or split) which is produced in the formation, the synthesis or the growth of the nanoparticles.
  • the nanoparticles as such (individual) have a mean size (diameter or greater dimension in the case of anisometric particles) which is preferably between 5 and 400 nm, more preferably within a range from 10 to 200 nm, in particular within a range from 10 to 100 nm (average calculated by number).
  • their mean size is preferably between 20 and 800 nm, more preferably within a range from 30 to 600 nm, in particular within a range from 40 to 400 nm (average calculated by number).
  • FSP sulphurization treatment of the invention the aim of which, it should be remembered, is to cause the surface metal to adhere firmly to a matrix of ethylenically unsaturated (thus crosslinkable with sulphur) polymer, a body (in particular a reinforcer, such as wire, cord, film or plate) having an at least partially metallic (in particular brass-coated) surface is obtained which can be described as “ready-for-use”: at this stage, this body or reinforcer is devoid of any polymer or rubber matrix at its periphery; it is ready for use as it is, without any adhesion primer or adhesion activator, such as a cobalt salt, as reinforcing element of an unsaturated rubber or polymer matrix, such as natural rubber.
  • a body in particular a reinforcer, such as wire, cord, film or plate
  • an at least partially metallic (in particular brass-coated) surface which can be described as “ready-for-use”: at this stage, this body or reinforcer is devoid of
  • FIG. 3 gives a diagrammatic representation of the anchoring of a rubber matrix ( 19 ) around the dendrites ( 18 ) previously formed by virtue of the FSP surface treatment, with an of course highly simplified representation of the metal/rubber interphase, once the surface ( 17 ) of the metal (M) has come into contact with the rubber matrix ( 19 ) (for example a rubber composition based on a diene elastomer, such as natural rubber) and once the assembly has been subsequently vulcanized.
  • the rubber matrix ( 19 ) for example a rubber composition based on a diene elastomer, such as natural rubber
  • a plate made of brass-coated (Cu/Zn: 60/40) carbon steel was subjected to an FSP treatment according to the invention, carried out using the device represented diagrammatically in FIG. 1 (closed glove box swept with a stream of nitrogen) in an atmosphere depleted in oxygen (O 2 content of the combustion chamber, measured immediately at the chamber outlet, of less than 100 ppm).
  • the plate with a thickness equal to approximately 3 mm (thickness of the brass layer of between 200 and 500 nm) was immobile and was treated for a period of time of 5 s at a distance “d” from the flame equal to approximately 70 mm.
  • the combustion chamber 1 was in this instance fed continuously with approximately 5 ml/min of pure thiophene (precursor P), 5 l/min of oxygen (oxidation gas 13 ) and a mixture of methane and oxygen (support gas 14 ) (CH 4 : 1.2 l/min; O 2 : 2.2 l/min).
  • the height of the flame (F) was between 6 and 7 cm and the temperature inside the flame was equal to approximately 700° C.
  • the combustion and the oxidation of the precursor P (thiophene) resulted in a gas composition, measured immediately at the chamber outlet by mass spectrometry (Pfeiffer Quadstar 100), which was as follows: approximately 10 ppm of H 2 S, 500 ppm of SO 2 , less than 100 ppm of O 2 , 1% of H 2 O, 1% of H 2 and 0.5% of CO 2 (mol %).
  • the thiophene was used in the state diluted (for example at 10% by weight) in an organic solvent (for example a mixture of 1 part of THF per 2 parts of 1,2-ethylhexanoic acid), this being done while keeping constant the ratio of the volume of dispersing gas (5 l/min of O 2 ) to the volume of fuel (5 ml/min of thiophene or of thiophene equivalent in the case of a dilution).
  • an organic solvent for example a mixture of 1 part of THF per 2 parts of 1,2-ethylhexanoic acid
  • the metal/rubber composite test specimen thus prepared was then placed under a press and the combination was cured at 165° C. for 30 min under a pressure of 20 bar.
  • FSP treatments in accordance with the invention have been carried out under the same flame conditions as above, this time on wires made of brass-coated carbon steel (diameter of approximately 0.30 mm) having high strength (for cords of “Steelcord” type for tyres).
  • these wires progressed forward continually, by virtue of a motorized robot, at a uniform speed (in this case, in these examples, at 60 cm/min) and at a distance “d” from the base of the flame which could vary automatically within a broad range of values.
  • FIG. 4 reproduces the three SEM photographs (5 kV; magnification 185 000) which were taken at the surface of the wires thus treated.
  • 1 cm is equivalent to approximately 200 nm (nanometres).
  • the surface of the wires thus treated was analysed by EDS (5 kV).
  • EDS Electronic Dispersive Spectroscopy
  • This EDS (Energy Dispersive Spectroscopy) technique makes it possible, it should be remembered, to determine the % by weight of each element present at the surface of the sample analysed. It has been used to measure the degree of sulphurization of the surface after the FSP treatment: for the three conditions above (respectively FIGS. 4A , 4 B and 4 C), the sulphur content measured was approximately 5.5%, 12% and 25% by weight respectively.
  • the analysis on an untreated control wire indicated the absence of sulphur (at any rate, below the detection limit).
  • FIG. 5 reproduces an SEM photograph (5 kV—magnification 100 000) taken at the surface of a plate made of brass-coated carbon steel identical to that of Test I but which has been subjected to a treatment in accordance with the invention this time comprising 2 consecutive FSP stages:

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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US14/653,517 2012-12-20 2013-12-16 Surface sulfurization of a metal body by flame spray pyrolysis Abandoned US20150307981A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1262411A FR3000107B1 (fr) 2012-12-20 2012-12-20 Sulfuration de surface d'un corps metallique par pyrolyse par projection de flamme
FR1262411 2012-12-20
PCT/EP2013/076713 WO2014095730A1 (fr) 2012-12-20 2013-12-16 Sulfuration de surface d'un corps metallique par pyrolyse par projection de flamme

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US10465273B2 (en) 2014-06-18 2019-11-05 Compagnie Generale Des Etablissements Michelin Surface graphenization of a metallic or metallized reinforcement by flame spray pyrolysis
US10655274B2 (en) 2014-06-18 2020-05-19 Compagnie Generale Des Etablissements Michelin Metallic or metallized, graphenized reinforcement
KR20210155644A (ko) * 2020-06-16 2021-12-23 한국화학연구원 표면 증강 라만 산란 기판용 황화구리 나노 소재 및 이의 제조방법
CN116495801A (zh) * 2023-04-28 2023-07-28 广东工业大学 一种中空球形的硫空位氧掺杂高熵硫化物纳米酶及其制备方法与poct应用

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CN106435464A (zh) * 2016-05-31 2017-02-22 青岛普雷斯马微波科技有限公司 柴油机自润滑缸套低温渗硫工艺

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KR102425293B1 (ko) * 2020-06-16 2022-07-26 한국화학연구원 표면 증강 라만 산란 기판용 황화구리 나노 소재 및 이의 제조방법
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FR3000107B1 (fr) 2015-05-01
FR3000107A1 (fr) 2014-06-27

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