WO1999020682A1 - Systemes et procedes permettant d'accroitre l'adherence interfaciale entre une surface metallique et un milieu non metallique, et produits ainsi obtenus - Google Patents

Systemes et procedes permettant d'accroitre l'adherence interfaciale entre une surface metallique et un milieu non metallique, et produits ainsi obtenus Download PDF

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Publication number
WO1999020682A1
WO1999020682A1 PCT/BE1998/000153 BE9800153W WO9920682A1 WO 1999020682 A1 WO1999020682 A1 WO 1999020682A1 BE 9800153 W BE9800153 W BE 9800153W WO 9920682 A1 WO9920682 A1 WO 9920682A1
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WO
WIPO (PCT)
Prior art keywords
group
metal
units
metal surface
tri
Prior art date
Application number
PCT/BE1998/000153
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English (en)
Inventor
Dries Declercq
Johan Vanbrabant
Daniel Mauer
Francis Garnier
Claude Nogues
Philippe Lang
Richard Michalitsch
Original Assignee
N.V. Bekaert S.A.
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
Application filed by N.V. Bekaert S.A. filed Critical N.V. Bekaert S.A.
Priority to AU95247/98A priority Critical patent/AU9524798A/en
Priority to EP98948629A priority patent/EP1025145A1/fr
Priority to EP99919271A priority patent/EP1137694A1/fr
Priority to PCT/EP1999/002904 priority patent/WO2000023504A1/fr
Priority to EP99924839A priority patent/EP1141098A1/fr
Priority to PCT/EP1999/002905 priority patent/WO2000023505A1/fr
Priority to AU41363/99A priority patent/AU4136399A/en
Publication of WO1999020682A1 publication Critical patent/WO1999020682A1/fr
Priority to US09/834,835 priority patent/US6830826B2/en
Priority to US09/834,420 priority patent/US6821632B2/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
    • E04C5/01—Reinforcing elements of metal, e.g. with non-structural coatings
    • E04C5/015—Anti-corrosion coatings or treating compositions, e.g. containing waterglass or based on another metal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the present invention concerns a method for improving the interfacial adhesion between a metal and a non-metallic medium, an interfacial adhesion promoter for use in said method and metal objects presenting improved interfacial adherence to non-metallic media.
  • Metal surfaces are often provided with organic coatings such as paints, varnishes and lacquers with a view to protecting the metal surfaces against mechanical damage or corrosion and/or to improve their appearance .
  • An alternative is to coat a metal surface with a plastic or rubber coating.
  • Metal elements such as wires, are also embedded in organic, e.g. rubber, or inorganic, e.g. cement or concrete, material for the reinforcement of the latter.
  • a primer coating is applied directly onto the metal surface, whereby said primer has an affinity both for the metal surface and for the non-metallic medium which is higher than the interfacial affinity between the metal and the non-metallic medium.
  • the non-metallic medium is subsequently applied onto the coated metal surface.
  • the primer should cover the metal surface entirely, leaving no part of it exposed.
  • Said primer coating preferably also possesses corrosion inhibiting properties.
  • Said known primer is obtained by first rinsing the metal surface with an alkaline silicate and aluminate solution and drying same to obtain an inorganically coated surface, whereafter the thus coated surface is rinsed with an aqueous solution of a hydrolyzed silane and a hydrolyzed cross linking agent. After drying a silane film is formed. The first, inorganic layer is said to confer onto the silane film an oriented molecular structure which is believed to improve the adhesion between the silane film and the paint to be applied thereto.
  • An example of a primer for metal-cement systems is known from international patent application WO 96/32522.
  • the method therein disclosed comprises the phosphatization of the metal surface in a Fe-, Ca/Zn- , Zn- or Mn-phosphate bath, followed by a surface treatment with an aqueous solution of pacifying compounds such as nitrites, chromates, hydrazine or hydrazine derivatives and hydroxylamines or hydroxylamine derivatives, and/or organic corrosion inhibitors.
  • pacifying compounds such as nitrites, chromates, hydrazine or hydrazine derivatives and hydroxylamines or hydroxylamine derivatives, and/or organic corrosion inhibitors.
  • the metal surface is initially freed of any scale and oxide, followed by depositing an insoluble amorphous or crystalline heavy metal phosphate coating on said surface, whereafter the surface is coated with a coating composition comprising an organic film forming medium, the composition of the coating being thus that it is chemically resistant to cement or concrete while simultaneously presenting high bond strength to both the cement or concrete and to the metal surface.
  • a coating composition comprising an organic film forming medium
  • the above-described metal-cement primer also provides corrosion protection to the metal surface.
  • a method for improving surface adhesion in a metal-rubber system is known from EP-A-738 748.
  • a stainless steel surface containing specific quantities of carbon, nickel and chromium and containing a minimum amount of martensite and a maximum amount of austenite, is first modified by means of an activation process whereby the metal surface is for example treated with an acid solution or by plasma treatment .
  • the thus activated metal surface is then treated with a silane film.
  • the preferred silane for use in this method is a bifunctional silane of the formula
  • the present invention aims to improve the adhesion between a metal surface and a range of non- metallic media.
  • the present invention can advantageously be used in the field of elastomer or cement reinforcement.
  • the present invention is more particularly useful for the reinforcement of elastomers and concrete, in particular high performance concrete by means of metal elements such as elongated steel elements .
  • Elongated steel elements for the reinforcement of elastomers such as tyres (rubber) , conveyor belts (rubber) , hoses (rubber) or timing belts (polyurethane or rubber) typically have the following features. As to their form, they are present as single steel filaments or steel wire, as twisted steel cord or as woven steel cord. The diameter of the individual steel filaments or steel wires range from 0.04 mm for the reinforcement of timing belts, to 2.0 mm for the reinforcement of the bead area of tyres.
  • the steel composition generally is along the following lines : a carbon content between 0.60 % by weight and 1.10 % by weight, a manganese content between 0.40 % by weight and 0.70 % by weight, a silicon content between 0.10 % by weight and 0.40 % by weight, a maximum sulfur content of 0.05 % by weight, a maximum phosphorus content of 0.05 % by weight.
  • Micro-alloying with particular elements such as chromium, nickel, vanadium, boron, cobalt, copper, molybdenum, etc. is not excluded for amounts ranging from 0.01 % by weight to 0.80 % by weight.
  • the steel wires or steel filaments are conveniently coated with a metallic layer such as brass
  • Elongated steel elements for the reinforcement of concrete have the form of steel fibres.
  • Such steel fibres typically have a length ranging from 3 mm to 60 mm, a thickness ranging from 0.08 mm to 1.20 mm and a tensile strength greater than 1000 MPa, e.g. greater than 1500 MPa, or greater than 2000 MPa.
  • the steel fibre is conveniently provided with anchorages for mechanically anchoring the fibre in the concrete.
  • the length-to-thickness ratio ranges between 50 and 200.
  • the concentration of the fibres in concrete may range from 25 kg/m 3 to 80 kg/m 3 .
  • thickness of a steel fibre refers to the smallest cross-sectional dimension of a straight steel fibre without the anchorages.
  • anchorage refers to any deviation from a straight steel fibre with a uniform transversal cross section where the deviation helps to improve the anchorage or staying of the steel fibre in the concrete.
  • the steel fibres have the same steel composition as for the reinforcement of elastomers.
  • the carbon content is lower than 0.60 % by weight since the tensile strength of the fibres is not so critical.
  • the steel fibres may or may not be provided with a metallic coating such as brass or zinc.
  • a metallic coating such as brass or zinc.
  • the reason for the metallic coating is not to create an improved adhesion with the concrete but rather to facilitate the final drawing steps or to provide a corrosion resistance.
  • “mortar” refer to concrete or mortar, the compression strength of which is higher than 75 MPa, e.g. higher than
  • the compression strength is the strength as measured by ASTM-Standard N° C39-80 on a cube of concrete of 150 mm edge, whereby the cube is pressed between two parallel surfaces until rupture.
  • high- performance concretes are characterized by : (a) a relatively low water/cement ratio (smaller than 0.45) ; (b) the addition of superplasticizers which much increase the workability of concrete in spite of the low water/cement ratio;
  • concrete and, more in particular, high performance concrete may also be reinforced by steel cables which may be prestressed.
  • the present invention concerns a primer composition for increasing the surface adhesion between a metal surface and a non-metallic medium.
  • Said primer composition comprises a practical amount of a bifunctional s coupling agent of formula X-R -Y.
  • a practical amount of s X-R -Y is meant, a concentration of said compound in the primer composition sufficient to produce a monolayer of s X-R -Y on the metal surface, given the primer application method used.
  • the constituent part X may be a
  • each -OR is the same and is a methoxy or an ethoxy group.
  • X may also be. a mono-, di- or tri-chlorosilane group or a mono-, di- or tri-bromosilane group.
  • X may be an acid function selected from the group comprising -CO 2 H, -PO 3 JH 2 ,and -SO 2 H, their acid anhydride and their acid chloride group.
  • X can also be an organometallic compound of the formula -M(OR) n , whereby M is a metal atom selected from the group comprising Al, Sn, B, Ti and V, and whereby each -OR is the same and is a methoxy or an ethoxy group, n being the ligand number corresponding to the metal M.
  • X can also be -MCl n , whereby M and n are as defined hereinabove.
  • X can furthermore be a phthalocyanin or a phthalonitril group.
  • X can also be a monothiol or a monothiolate group.
  • Constituent part R may be a -(CH2) n _ chain, whereby 2 ⁇ n ⁇ 20 and whereby said chain may be unsubtituted, partially halogenated or perhalogenated.
  • R may be a continuous chain consisting of: n partially halogenated or perhalogenated -(CH 2 )- units,
  • Constituent part R may further be a chain
  • Constituent part Y may be an unsaturated terminal carbon-carbon double or triple bond.
  • Y can also be an acrylic or methacrylic acid group and its methyl or ethyl esters.
  • Y may be of the form -NH 2 or -NHR, whereby R is a methyl or ethyl group.
  • Y can further be an activated carboxylic ester group .
  • Y can be an aldehyde group.
  • Y can be an epoxide group.
  • Y ⁇ an be any one of the following: ⁇ H ⁇ --- H __ ⁇ -0R
  • each OR is the same and is a methoxy or an ethoxy group.
  • Y can be a mono-, a di- or a tri- chlorosilane group or a mono-, di- or tri-bromosilane group.
  • R When Y is an alkoxysilane group, a chloro- or s bromosilane group, R must be a -(CH 2 , 3 - or a - (CH2) 4 - chain which may be unsubstituted, partially halogenated or perhalogenated.
  • Y may be a functional group capable of forming a complex with at least one ingredient of the non-metallic medium concerned.
  • This ingredient may be present in the non-metallic medium as such, for example as a pigment, or may have been added to the non-metallic medium specifically so as to allow the formation of a complex with constituent part Y.
  • Y may be -Si-OH or -Si-ONa.
  • chloride-containing constituent parts X such as -MCl n and -SiCl 3 may provide high quality adhesion to the metal surface
  • the use of s chloride containing constituent parts X, R and Y is contra- indicated if the metal surface is liable to corrode in the presence of chloride ions. This is specifically the case with steel or iron-containing metal surfaces.
  • X is an alkoxysilane
  • X is preferably a trimethoxysilane or a triethoxysilane group.
  • X is a monothiolate group, it is preferably -SNa or -SK.
  • R is an unsubstituted, partially halogenated or perhalogenated -(CH 2 ) n ⁇ chain, optionally 2 ⁇ n ⁇ 16 or 2 ⁇ n ⁇ 10.
  • n is preferably equal to or greater than 4 and most preferably situated between 6 and 12, the values 6 and 12 being included.
  • R is an unsubstituted, partially halogenated or perhalogenated -(CH 2 ) n - chain, n > 12.
  • the halogenation is preferably a fluorination. A perfluorinated -(CH 2 ) n - chain is most preferred.
  • R is a continuous chain consisting of: n partially halogenated or perhalogenated -(CH2)- units.
  • constituent and/or units may be adjacent constituent part X, adjacent constituent part Y or may be attached to constituent part X and/or to constituent part Y via one or more of the -(CH2)- units.
  • constituent part Y is a terminal double carbon-carbon bond then R can advantageously be such that s -R -Y terminates in any one of the following groups: vinyl, allyl, styryl, thienylvinylene, phenyl or pyrrole groups. If Y is an alkoxysilane, Y is preferably a trimethoxysilane or triethoxysilane group.
  • Y is an activated carboxylic ester group of the formula 0
  • crown and aza crown ethers consisting of 4 , 5 or 6 -OCH 2 CH 2 - units .
  • the present invention equally concerns a metal element having at least part of its metal surface covered with an organic monolayer obtained by reaction of a s bifunctional coupling agent of the formula X-R -Y on the s metal surface, whereby X-R -Y is as described hereinabove.
  • Such a metal element presents advantageous surface adhesion properties with regard to one or more of a range of non- metallic media.
  • the metal surface of the metal element according to the invention may mainly be made of Al, Fe, Ni, Cu, Zn, Ag or alloys of these metals.
  • the metal element according to the invention may consist of a basic metal element which is coated with a metal coating of a brass, bronze, zinc or zinc alloy and whereby the said metal surface is formed by said coating.
  • the basic metal element may be made out of steel.
  • the constituent part X may advantageously be one of the following: a)
  • each -OR is the same and is a methoxy or an ethoxy group, b) mono-, di- and tri-chlorosilane groups or mono-, di- or tri-bromosilane groups, c) -CO 2 H, -PO 3 H 2 , -SO 2 H, their anhydride and acid chloride group, d) a monothiol or a monothiolate group, or e) a phthalocyanin or a phthalonitril group.
  • the constituent part X is preferably : a) -M[OR] n , whereby M is Al, Ti, V, B or Sn and whereby each -OR is the same and is a methoxy or an ethoxy group,
  • each -OR is the same and is a methoxy or an ethoxy group, c) a chloro- or bromosilane group, d) -CO2H, -PO3H 2 , or -SO 2 H.
  • the constituent part X is preferably : a) a phthalocyanin or a phthalonitril group,
  • constituent part X is preferably one of the following : a)
  • constituent part X is advantageously on of the following :
  • constituent part Y may be -NH 2 or -NHR, whereby -R is a methyl or an ethyl group.
  • -R is a methyl or an ethyl group.
  • This embodiment of the present invention is particularly indicated when the part of the metal surface which is covered with the monolayer is further covered with a polyurethane coating.
  • the metal element is an s elongated metal element and the constituent part Y of X-R -Y is -NH 2 or
  • such an elongated element can advantageously be used for the reinforcement of polyurethane.
  • constituent part Y is a double or triple carbon-carbon bond, including those embodiments whereby s -R -Y terminates in a vinyl, an allyl, a styryl, a thienylvinylene, a phenyl or a pyrrole group
  • the part of the metal surface which is covered with the monolayer is advantageously further covered with a polyethylene, polypropylene, polybutadiene, a copolymer of at least two of ethylene, propylene and butadiene, or a rubber coating.
  • constituent part Y is of this type, elongated metal elements according to the invention coated with such an s X-R -Y monolayer can advantageously be used for the reinforcement of polyethylene, polypropylene, polybuta- diene, a copolymer of at least two of ethylene, propylene and butadiene, and rubber.
  • each -OR group is the same and is a methoxy or an ethoxy group, or, if the metal surface so allows, a mono-, di- or tri-chlorosilane group or a mono-, di- or s tri-bromosilane group, and whereby R is a straight -(CH 2 13- or -(CH 2 )_- alkyl chain, which may be unsubstituted, partially halogenated or perhalogenated, the part of the metal surface which is covered with the monolayer is advantageously further covered with a siloxane coating.
  • fluorinated, and particularly perfluorinated alkyl chains are preferred.
  • constituent part Y is an activated ester group, and in particular when Y is
  • the part of the metal surface which is covered with the monolayer is advantageously further covered with a polyacrylate coating.
  • an elongated metal element according to the invention the surface of which is covered with a monolayer of X-R -Y can advantageously be used for the reinforcement of a polyacrylate.
  • constituent part Y is an ion complexing group capable of forming a complex with an ingredient of concrete, in particular when Y is HO 2 CCO 2 H, (H ⁇ 2CCH2)NCH2CH 2 N(CH2C0 2 H)2 [-CH 2 0 (CH 2 CH 2 0) n CH 3 whereby
  • Complexing constituent parts Y may also be used when the metal element is to be coated with or incorporated in a non-metallic medium comprising a sufficiently high concentration of ingredients, such as pigments, with which the complexing group Y can form a stable complex.
  • Bifunctional coupling agents of the present invention present the important tendency of forming Self- Assembled Monolayers on the metal surface, i.e. when applied onto the metal surface, then the molecules automatically tend to form a structured, packed monolayer whereby the constituent parts X are attached to the metal surface and whereby the substituent parts Y point away from the metal surface.
  • This property of the bifunctional s coupling agents X-R -Y provides an important contribution to the ef ectiveness of the coupling agent and allows for an easy realisation of the monolayer onto the metal surface.
  • Methods for preparing molecules corresponding to the bifunctional coupling agents according to the present invention are known from the state of the art. Many are moreover commercially available. By way of example, a preparation method is described hereinbelow for three of the bifunctional coupling agents according to the present invention.
  • NBS 0.055 mole n-bromosuccinimide
  • Chromatographic control showed that the reaction was finished after one hour.
  • the product was extracted with several portions of ether.
  • the etherous solution was washed with NaHC0 3 , dried with MgS0 4 and the ether evaporated.
  • the liquid product was purified using column chromatography over silica (70-200 mesh) . Elution with hexane gave 14.9 g (92 %) 6- (5-bromothien-2-yl) bromohexane (compound 4) .
  • the product was used without further purification.
  • the bromination procedure was repeated on the other terminal ⁇ -position using once more NBS in dimethylformamide and resulting in the formation 5-vinyl, 5'bromo--2, 2 ' -biothiophene, which was subsequently converted to the corresponding Grignard compound by adding 0.02 mole (3.8 g) of the brominated product to 0.5 g magnesium turnings in 100 ml ether.
  • the reaction solution was gently refluxed for 2 hours and subsequently transferred to another experimental set.
  • the Grignard solution was slowly dropped into a mixture of 8.15g
  • Phosphonic acids (often called phosphonates) were prepared by Michaelis-Arbuzov reaction of the corresponding haloalkanes with triethyl-phosphite, 0.02 mole (2.98 g) of
  • the present invention also concerns a method of treating a metal surface with the bifunctional coupling agent X-R s -Y.
  • Said method comprises the step of applying a monolayer of X-R -Y onto a metal surface.
  • the metal surface can be coated with primer composition which is a suitable solution of X-R -Y. This can be effected by dipping, spraying, electrochemical deposition or other known coating techniques.
  • the monolayer can also be formed by vapour deposition of X-R -Y on the metal surface.
  • An alternative method is plasma deposition. s
  • HREELS High Resolution Electron Energy Loss
  • the metal surface should be covered with a closely packed monolayer and not more than a monolayer.
  • s Excess X-R -Y present on the metal surface should be removed before applying the non-metallic coating onto the metal surface or before incorporating the metal element into the non-metallic medium e.g. for reasons of s reinforcement. Removal of excess X-R -Y can be performed by known techniques, such as by vacuum treatment, by rinsing the metal surface with a suitable solvent followed by drying, or by ultrasonic rinsing.
  • Side-products may be produced during deposition s of the X-R -Y monolayer on the metal surface. This is for example the case when constituent part X is a alkoxysilane group.
  • ROH whereby -OR is an alkoxy group of the alkoxysilane, is then produced as a side-product of the surface chemisorption reaction.
  • side-products are liable to disturb the regular structure of the monolayer, they must as much as possible, be eliminated from the metal surface and the monolayer.
  • bifunctional coupling agents of the present invention present the important tendency of forming Self-Assembled Monolayers on the metal surface. s
  • anomalies may be present. These anomalies are preferably eliminated from the monolayer by means of a thermal tempering treatment, at a temperature depending on the chemical nature of the constituent part X group (e.g. when
  • tempering may be conducted at ⁇ 200°C; when X is a thiol group tempering may be conducted at
  • Such cleaning can be effected by a known thermal, mechanical or chemical cleaning process or a combination of such processes, which could for instance be a descaling process.
  • molecules of the above-defined formula s X-R -Y allow to realize a strong and lasting adhesion between, on the one hand, a range of metal surfaces and, on the other hand, a range of non-metallic media, by means of a purposeful selection of all three of the constituent parts X, R and Y .
  • the concentration of the constituent parts Y on the surface of the monolayer not attached to the metal surface must be high.
  • An additional important advantage of the present invention is that it effectively inhibits corrosion of the metal surface through the presence of the constituent parts X on the metal surface and through the close packing of the layer.
  • the said corrosion inhibiting effect is further s enhanced when constituent part R is fluorinated.
  • -(CH 2 ) n - n may vary between 2 and 20, preferably between 4 and 20.
  • n ⁇ 10 allows for an electrochemical s activation from the metal, via X and R , to constituent part Y for the coupling of Y to the non-metallic medium.
  • a high value of n (>12) provides for better corrosion inhibition by passivation and blocking of the metal surface.
  • Halogenation -preferably fluorination- of said - (CH2)n- chains not only increases corrosion inhibition due to increased hydrophobicity, it also confers lubrification properties on the monolayer. In many applications this is a significant advantage for the further processing of the metal element.
  • Step 1 Hydrolysis of an amount of 3-Amino-propyl- trimethoxysilane (APTS) (I) .
  • APTS 3-Amino-propyl- trimethoxysilane
  • Step 2 Hydrolysis of the surface active silane
  • step 1 [6- (p-styryl) hexyltrimethoxysilane].
  • the solution obtained from step 1 is diluted with 9 ml of methanol and 1 ml of water. 9 ml of the surface active coupling agent II are added under stirring at 60°C. The solution is ready for use after 5 minutes. This solution is further diluted to 1 1 with methanol to yield a final solution of 1 % of II.
  • Zinc coated steel cords are dipped for 1 second in the above solution and dried for lOminutes at 65°C.
  • the coated steel cords are subsequently embedded in a natural rubber compound.
  • the composite is put in a rubber curing press for 20 minutes at a temperature of 150°C.
  • Step 1 A zinc coated steel cord in rinsed with demineralised water. The sample is subsequently dipped for two seconds in a 0.5 % HN0 3 solution.
  • the sample is rinsed again with demineralised water and further dipped in a 1.5 %
  • Step 2 The sample prepared as in step 1, is now dipped for twenty seconds in a solution of an anorganic silicate : Corosil® 401 (150 ml/1) + Corrosil®
  • Step 3 The sample as prepared in step 2, is now dipped for 60 seconds in a 3 % primer solution of
  • Step 1 A sample is dipped during 2 seconds in a solution (100 g/1) of (NH ) 6Mo 7 0 24 .4H 2 0 under a
  • the counter electrode is a plate of stainless steel.
  • the sample is subsequently rinsed with demi water and dried with ethanol and ether.
  • Molybdenum is supplied to the surface of the steel cord.
  • Steps 2 and 3 same as for sample n° 1.
  • Sample n° 3 type of preparation : Electrochromatation.
  • Step 1 A sample is dipped during three seconds in an electrochemical cell at 50°C containing the following electrolyte (50 g/1) : K 2 Cr 2 ⁇ 7 ; 30 g/1 ZnS0 4 and 20 ml/1 acetic acid. Current density is about 70 A/dm 2 . Voltage is 2.5 V. The counter electrode is a platina electrode. The sample is subsequently rinsed with demi water and dried in ethanol and ether. This pre- treatment provides for chromium on the steel cord.
  • Steps 2 and 3 same as f.or sample n° 1.
  • Step 1 same as for sample n° 1
  • Step 2 The sample as prepared in step 1 is dipped during twenty seconds in a solution of bistriethoxysilyl ethane (BTSE) (4% BTSE + 20% water in absolute ethanol ; pH : 5.5-6.5) The sample is dried in the air during three minutes and finally dried at 70°C during ten minutes.
  • BTSE bistriethoxysilyl ethane
  • Step 3 same as for sample n° 1
  • Sample n° 5 type of preparation : electrochemical molybdenisation.
  • Step 1 same as for sample n 2 Step 2 same as for sample n° 4 Step 3 same as for sample n° 1
  • Step 1 same as for sample n 3 Step 2 same as for sample n° 4 Step 3 same as for sample n° 1
  • Step 3 The sample as prepared in step 2, is dipped during 60 seconds in a 3 % primer solution of 3-mercaptopropyl triethoxysilane (MPTS) in absolute ethanol containing 5 ml NaOH (final pH : 8.49). The sample is further dried in the air during five minutes and finally dried during 10 minutes at 60°C.
  • MPTS 3-mercaptopropyl triethoxysilane
  • Step 1 same as for sample n° 1 Step 2 is omitted Step 3 same as for sample n° 7
  • APTS 3-amino-propyl-trimethoxysilane
  • a prereaction or hydrolysis of silanes is preferably done, prior to the use of the solution. This is done on the pure silane before dilution. The following steps are followed to hydrolyse the silane :
  • a 40 % solution of sodium silicate with 5 % of silane is made by mixing 400 ml of silicate with 200 ml of water. Hydrolysed silane, as prepared hereabove, is added to an end concentration of 5 % silane. Adjust with water to reach 1000 ml. The end concentration of the primer solution is then 40 % Na 2 Si0 3 with 5 % silane. The primer solution can be used pure or diluted 1/2 with water.
  • silane triethoxysilyl poly-1,2 butadiene. This silane is dissolved under reflux in heptane/toluene 10:1. The wire is dipped in a boiling solution, dried during one hour in air followed by a drying step of 15 minutes at 110 °C.
  • the adhesion strength is quantified by the pull out force as per ASTM D2229.
  • cord or wire is embedded in polyurethane and the force necessary to pull the elements linearly out of the polyurethane is measured.
  • the embedded length of the sample is 25 mm.
  • the pull out speed is 100 mm/min and the circle of the pull out clamp is 12.7 mm.
  • Prior art stands for untreated zinc coated steel cord.
  • the composition of the rubber is : natural rubber : 100 parts, carbon black N300 : 60 parts per hundred rubber (phr) , oil : 11 phr, zinc oxide : 5 phr, stearic acid : 1 phr, 6-ppd : 1 phr, sulphur : 2.5 phr, MBS : 0.6 phr.
  • Adhesion is quantified by the pull out force as per ASTM D2229.
  • the embedded length is 25 mm.
  • the vulcanisation temperature was 150°C and vulcanisation time was 20 minutes.
  • the pull out speed is 100 mm/min, and the circle of the pull out clamp is 12.7 mm.
  • Prior art stands for untreated zinc coated steel cord.
  • the embedded length is here 40 mm.
  • the pull out speed is 50 mm/min.
  • Prior art stands for untreated zinc coated steel cord.
  • the prereaction or hydrolysis of silanes is preferably done, prior to the use of the primer solution. This is done on the pure silane before dilution. The steps given in samples 9 and 10 above are followed to hydrolyze the silane.
  • Step 1 Hydrolysis of a effective amount of 3-amino- propyl-trimethoxysilane (APTS) .
  • Step 2 A 40 % solution of sodium silicate with 5 % of silane is made by mixing 400 ml of silicate with 200 ml of water. Hydrolysed silane, as prepared in step 1, is added to an end concentration of 5 % silane. Adjust with water to reach 1000 ml. The end concentration of the solution is then
  • the primer solution can be used pure or diluted 1/2 with water.
  • MPTS 3-mercapto-propyl- trimethoxysilane
  • APTS 3-amino-propyl- trimethoxysilane
  • the adhesion strength is measured as the pull out force of a straight wire out of concrete.
  • the electrolyte 0.1 N sulphuric acid is substituted with 0.05 molar potassium sulphate.
  • the polarisation scan is carried out after 1000 seconds instead of after 1 hour of immersion.
  • the polarisation resistance R p and the corrosion current density Icorr is calculated in accordance with ASTM G3-89 and ASTM G102-89.
  • the so called “inhibiting rating” is calculated as defined in "Compendium of Chemical Terminology", IUPAC Recommendations, Blackwell Scientific Publications, 1987, p 198 :
  • Prior art sample 14 galvanized wire for bead reinforcement .
  • Sample n° 15 galvanized wire for bead reinforcement treated with 1/3 concentration of 3-aminopropyltrietoxysilane.
  • Prior art sample 16 galvanized steel cord.
  • Sample n° 17 galvanized steel cord treated with 1/3 concentration of 3-aminopropyltrietoxysilane.
  • Sample n° 19 zinc plated steel cord treated with 0.01 solution of 3-aminopropyltriethoxysilane (APTS) .
  • Sample n° 20 zinc plated steel cord treated with 0.1 ' ⁇ solution of 3-aminopropyltriethoxysilane (APTS) .
  • Sample n° 21 zinc plated steel cord treated with 1 % solution of 3-aminopropyltriethoxysilane (APTS) .
  • Sample n° 22 zinc plated steel cord treated with 1 % solution of (3-methoxysilylpropyl) diethylenetriamine.
  • the corrosion potential is the potential of a corroding surface in an electrolyte relative to a reference electrode measured under open circuit conditions (source : ASTM G15-93) .
  • the value below which hydrogen may be formed lies somewhere between -1000 mV and -1100 mV.

Abstract

Cette invention concerne des systèmes et des procédés permettant d'accroître l'adhérence interfaciale entre une surface métallique et un milieu non métallique. A cette fin, on utilise un agent de couplage bifonctionnel qui possède une première fonction d'extrémité assurant l'adhérence à la surface métallique, ainsi qu'une seconde fonction d'extrémité assurant l'adhérence au milieu non métallique. Les deux groupes fonctionnels de l'agent de couplage sont séparés l'un de l'autre par un groupe d'espacement. Cette invention concerne également des éléments métalliques qui sont enrobés de cet agent de couplage bifonctionnel, ainsi que des éléments métalliques ainsi enrobés qui sont recouverts d'un milieu non métallique. Cet invention concerne enfin l'utilisation de ces éléments enrobés en qualité d'éléments de renfort.
PCT/BE1998/000153 1997-10-22 1998-10-15 Systemes et procedes permettant d'accroitre l'adherence interfaciale entre une surface metallique et un milieu non metallique, et produits ainsi obtenus WO1999020682A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
AU95247/98A AU9524798A (en) 1997-10-22 1998-10-15 Means and methods for enhancing interfacial adhesion between a metal surface anda non-metallic medium and products obtained thereby
EP98948629A EP1025145A1 (fr) 1997-10-22 1998-10-15 Systemes et procedes permettant d'accroitre l'adherence interfaciale entre une surface metallique et un milieu non metallique, et produits ainsi obtenus
EP99919271A EP1137694A1 (fr) 1998-10-15 1999-04-22 Element metallique de renfort et procedes d'enrobage associes
PCT/EP1999/002904 WO2000023504A1 (fr) 1998-10-15 1999-04-22 Composite de caoutchouc vulcanisable, composition de caoutchouc, et produit de caoutchouc vulcanise
EP99924839A EP1141098A1 (fr) 1998-10-15 1999-04-22 Composite de caoutchouc vulcanisable, composition de caoutchouc, et produit de caoutchouc vulcanise
PCT/EP1999/002905 WO2000023505A1 (fr) 1998-10-15 1999-04-22 Element metallique de renfort et procedes d'enrobage associes
AU41363/99A AU4136399A (en) 1998-10-15 1999-04-22 Composite of a vulcanizable rubber composition and cured rubber product
US09/834,835 US6830826B2 (en) 1998-10-15 2001-04-13 Coated metal reinforcement element and coating materials
US09/834,420 US6821632B2 (en) 1998-10-15 2001-04-13 Composite of a vulcanizable rubber composition and cured rubber product

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP97870163 1997-10-22
EP97870163.9 1997-10-22

Publications (1)

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Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6261638B1 (en) 1997-01-09 2001-07-17 University Of Cincinnati Method of preventing corrosion of metals using silanes
US6416869B1 (en) 1999-07-19 2002-07-09 University Of Cincinnati Silane coatings for bonding rubber to metals
WO2004059036A2 (fr) * 2002-12-23 2004-07-15 Basf Aktiengesellschaft Composes hydrophobes-hydrophiles destines au traitement de surfaces metalliques
US6777081B2 (en) 1999-12-15 2004-08-17 N.V. Bekaert S.A. Reinforcing structure for stiff composite articles
US6787491B2 (en) 1999-12-15 2004-09-07 N.V. Bekaert S.A. Woven composite fabric
FR2853660A1 (fr) * 2003-04-09 2004-10-15 Michelin Soc Tech Composite(metal/caoutchouc)pour pneumatique
US6827981B2 (en) 1999-07-19 2004-12-07 The University Of Cincinnati Silane coatings for metal
US6883843B2 (en) 2002-03-08 2005-04-26 N.V. Bekaert S.A. Reinforced impact beam
US6887806B2 (en) 2000-05-11 2005-05-03 N.V. Bekaert S.A. Cut resistant fabric for protective textiles
US6920745B2 (en) 2000-05-08 2005-07-26 N.V. Bekaert S.A. Zinc-coated steel cord with improved fatigue resistance
WO2006015010A2 (fr) * 2004-07-30 2006-02-09 General Electric Compamy Compositions de silane, procedes de preparation de ces compostions de silane et compositions de caoutchouc renfermant ces dernieres
US7111882B2 (en) 2002-03-08 2006-09-26 N. V. Bekaert S.A. Reinforced impact beam with woven fabric
US7368584B2 (en) 2006-08-14 2008-05-06 Momentive Performance Materials Inc. Mercapto-functional silane
US7504456B2 (en) 2006-02-21 2009-03-17 Momentive Performance Materials Inc. Rubber composition containing organofunctional silane
US7510670B2 (en) 2006-02-21 2009-03-31 Momentive Performance Materials Inc. Free flowing filler composition based on organofunctional silane
US7550540B2 (en) 2006-08-14 2009-06-23 Momentive Performance Materials Inc. Rubber composition and articles therefrom both comprising mercapto-functional silane
US7566486B2 (en) 2000-05-31 2009-07-28 Nv Bekaert Sa Braid reinforced flexible hose
US7919650B2 (en) 2006-02-21 2011-04-05 Momentive Performance Materials Inc. Organofunctional silanes and their mixtures
WO2011067137A1 (fr) 2009-12-01 2011-06-09 Nv Bekaert Sa Composite de polymère renforcé
WO2012055895A1 (fr) * 2010-10-27 2012-05-03 Shell Internationale Research Maatschappij B.V. Béton armé au soufre
WO2013041255A1 (fr) 2011-09-21 2013-03-28 Nv Bekaert Sa Fils câblés qui ne s'ancrent pas à une liaison non chimique avec la matrice dans une poutrelle anti-choc
WO2013041254A1 (fr) 2011-09-21 2013-03-28 Nv Bekaert Sa Dispositif de maintien de distance sans acier dans une poutre pare-chocs
CN103387694A (zh) * 2013-08-14 2013-11-13 王谷安 一种钢丝及生产方法和含钢丝骨架的橡胶制品
US9293511B2 (en) 1998-07-08 2016-03-22 E Ink Corporation Methods for achieving improved color in microencapsulated electrophoretic devices
EP2802707A4 (fr) * 2012-01-12 2016-05-11 Otis Elevator Co Revêtement protecteur pour cordes

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EP0383150A1 (fr) * 1989-02-17 1990-08-22 Compagnie Generale Des Etablissements Michelin-Michelin & Cie Procédés pour traiter un renfort métallique de façon à favoriser son adhesion à une composition à base de caoutchouc et pour réaliser un article avec ce renfort; renforts et articles obtenus avec ces procédés
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EP0738748A1 (fr) * 1995-03-29 1996-10-23 Compagnie Generale Des Etablissements Michelin-Michelin & Cie Procédé pour traiter un corps en acier inoxydable de façon à favoriser son adhésion à une composition de caoutchouc
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EP0331279A2 (fr) * 1988-02-15 1989-09-06 Zeneca Limited Composés et leur utilisation
EP0383150A1 (fr) * 1989-02-17 1990-08-22 Compagnie Generale Des Etablissements Michelin-Michelin & Cie Procédés pour traiter un renfort métallique de façon à favoriser son adhesion à une composition à base de caoutchouc et pour réaliser un article avec ce renfort; renforts et articles obtenus avec ces procédés
US5126385A (en) * 1990-03-20 1992-06-30 Uniroyal Chemical Company, Inc. Chloropyrimidines and chlorotriazines as rubber-to-metal adhesion promoters
EP0738748A1 (fr) * 1995-03-29 1996-10-23 Compagnie Generale Des Etablissements Michelin-Michelin & Cie Procédé pour traiter un corps en acier inoxydable de façon à favoriser son adhésion à une composition de caoutchouc
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Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6261638B1 (en) 1997-01-09 2001-07-17 University Of Cincinnati Method of preventing corrosion of metals using silanes
US9293511B2 (en) 1998-07-08 2016-03-22 E Ink Corporation Methods for achieving improved color in microencapsulated electrophoretic devices
US6827981B2 (en) 1999-07-19 2004-12-07 The University Of Cincinnati Silane coatings for metal
US6416869B1 (en) 1999-07-19 2002-07-09 University Of Cincinnati Silane coatings for bonding rubber to metals
US6756079B2 (en) 1999-07-19 2004-06-29 The University Of Cincinnati Silane coatings for bonding rubber to metals
US6955728B1 (en) 1999-07-19 2005-10-18 University Of Cincinnati Acyloxy silane treatments for metals
US6919469B2 (en) 1999-07-19 2005-07-19 The University Of Cincinnati Silane coatings for bonding rubber to metals
US6787491B2 (en) 1999-12-15 2004-09-07 N.V. Bekaert S.A. Woven composite fabric
US6777081B2 (en) 1999-12-15 2004-08-17 N.V. Bekaert S.A. Reinforcing structure for stiff composite articles
US7304007B2 (en) 1999-12-15 2007-12-04 Nv Bekaert Sa Woven composite fabric
US6920745B2 (en) 2000-05-08 2005-07-26 N.V. Bekaert S.A. Zinc-coated steel cord with improved fatigue resistance
US6887806B2 (en) 2000-05-11 2005-05-03 N.V. Bekaert S.A. Cut resistant fabric for protective textiles
US7566486B2 (en) 2000-05-31 2009-07-28 Nv Bekaert Sa Braid reinforced flexible hose
US6883843B2 (en) 2002-03-08 2005-04-26 N.V. Bekaert S.A. Reinforced impact beam
US7007990B2 (en) 2002-03-08 2006-03-07 N.V. Bekaert S.A. Reinforced impact beam with layered matrix
US7111882B2 (en) 2002-03-08 2006-09-26 N. V. Bekaert S.A. Reinforced impact beam with woven fabric
WO2004059036A3 (fr) * 2002-12-23 2005-03-17 Basf Ag Composes hydrophobes-hydrophiles destines au traitement de surfaces metalliques
WO2004059036A2 (fr) * 2002-12-23 2004-07-15 Basf Aktiengesellschaft Composes hydrophobes-hydrophiles destines au traitement de surfaces metalliques
WO2004090023A1 (fr) * 2003-04-09 2004-10-21 Societe De Technologie Michelin Composite metal/ caoutchouc pour pneumatique
FR2853660A1 (fr) * 2003-04-09 2004-10-15 Michelin Soc Tech Composite(metal/caoutchouc)pour pneumatique
JP2008508295A (ja) * 2004-07-30 2008-03-21 ゼネラル・エレクトリック・カンパニイ シラン組成物、その調製法とそれを含むゴム組成物
US7531588B2 (en) 2004-07-30 2009-05-12 Momentive Performance Materials Inc. Silane compositions, processes for their preparation and rubber compositions containing same
WO2006015010A3 (fr) * 2004-07-30 2006-07-20 Gen Electric Compositions de silane, procedes de preparation de ces compostions de silane et compositions de caoutchouc renfermant ces dernieres
WO2006015010A2 (fr) * 2004-07-30 2006-02-09 General Electric Compamy Compositions de silane, procedes de preparation de ces compostions de silane et compositions de caoutchouc renfermant ces dernieres
US7504456B2 (en) 2006-02-21 2009-03-17 Momentive Performance Materials Inc. Rubber composition containing organofunctional silane
US7510670B2 (en) 2006-02-21 2009-03-31 Momentive Performance Materials Inc. Free flowing filler composition based on organofunctional silane
US7919650B2 (en) 2006-02-21 2011-04-05 Momentive Performance Materials Inc. Organofunctional silanes and their mixtures
US7368584B2 (en) 2006-08-14 2008-05-06 Momentive Performance Materials Inc. Mercapto-functional silane
US7550540B2 (en) 2006-08-14 2009-06-23 Momentive Performance Materials Inc. Rubber composition and articles therefrom both comprising mercapto-functional silane
US20120238685A1 (en) * 2009-12-01 2012-09-20 Nv Bekaert Sa Reinforced polymer composite
CN102667025A (zh) * 2009-12-01 2012-09-12 贝卡尔特公司 增强聚合物复合材料
CN102667025B (zh) * 2009-12-01 2014-12-31 贝卡尔特公司 增强聚合物复合材料
WO2011067137A1 (fr) 2009-12-01 2011-06-09 Nv Bekaert Sa Composite de polymère renforcé
WO2012055895A1 (fr) * 2010-10-27 2012-05-03 Shell Internationale Research Maatschappij B.V. Béton armé au soufre
CN103180261A (zh) * 2010-10-27 2013-06-26 国际壳牌研究有限公司 增强硫磺混凝土
US8753444B2 (en) 2010-10-27 2014-06-17 Shell Oil Company Reinforced sulphur concrete
AU2011322608B2 (en) * 2010-10-27 2015-01-22 Shell Internationale Research Maatschappij B.V. Reinforced sulphur concrete
WO2013041255A1 (fr) 2011-09-21 2013-03-28 Nv Bekaert Sa Fils câblés qui ne s'ancrent pas à une liaison non chimique avec la matrice dans une poutrelle anti-choc
WO2013041254A1 (fr) 2011-09-21 2013-03-28 Nv Bekaert Sa Dispositif de maintien de distance sans acier dans une poutre pare-chocs
US9102288B2 (en) 2011-09-21 2015-08-11 Nv Bekaert Sa Non-anchoring cords with non-chemically binding with the matrix in impact beam
EP2802707A4 (fr) * 2012-01-12 2016-05-11 Otis Elevator Co Revêtement protecteur pour cordes
CN103387694A (zh) * 2013-08-14 2013-11-13 王谷安 一种钢丝及生产方法和含钢丝骨架的橡胶制品

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