Method for producing metal-polymeric coating

FIELD: metal processing.

SUBSTANCE: invention refers to processing of polymeric functional materials and can be used in machine building at coating of machine and aggregate units and units of transport systems, mainly pipes for transmission of oil products. The method for producing metal-polymeric coating consists in mixing polymer particles in a powdered form and metal containing precursor particles in a powdered form. Then a powdered mixture is settled on the surface of a unit and heated; polymer particles are melted. After that, thermolysis of the precursor and monolithic integration of coating are carried out. Polymer particles in a powdered form are selected out of a group containing polyamide, polyethylene terephthalate and polyethylene of high pressure. Particles in a powdered form of metal containing precursor represent formate or oxalate of copper, nickel, zinc or carbonyl iron. Heating, melting of polymer particles and thermolysis of precursor are carried out simultaneously in a thermo gas flow with a density of 3·106 -9·106 Wt/m2 within 10-4-10-3 sec. The mixture is settled and monolithic integration of coating is performed on the unit heated to a temperature of T=Tm+5÷40°C, where Tm is the temperature of polymer melting at the density of the gas flow of 3-5 atm.

EFFECT: method allows for high processibility and upgrading of adhesion hardness, strength and rupture strength at tension.

2 tbl

 

The invention relates to the field of technology of functional polymer materials and can be used in mechanical engineering for applying coatings on machine parts, machinery and transport systems, primarily pipelines for transporting petroleum products.

Polymer coatings of different composition is applied to the details of the units of machines and mechanisms to ensure the specified functions - reduce wear, reduce friction, provide the necessary insulating characteristics, corrosion resistance, etc. (Dovgalo VA, Yurkevich O.R. Composite materials and coatings based on dispersed polymer. - Minsk: Science and technology. - 1992. - s). As the polymer matrix used polyamides, Polyacetals, polyolefins, polyurethanes and other thermoplastic and Thermoelastoplastic matrix. To ensure the specified functional characteristics of the coating to the polymeric matrix is injected fillers and modifiers: powders of oxides, metals, dry lubricants, wood and other components.

Among the most common methods of applying functional polymer coatings, along with the mortar technology, fluidized bed technology, according to which you can apply coatings of different composition on the surfaces of metal parts.

Modifiers and fillers p. the polymer matrix have a decisive influence on the performance characteristics of composite materials based on them. The most common modifiers are polymer matrices of different composition and structure of the mineral components are obtained by processing natural semi-finished products: clays, micas, zeolites, etc. Received mineral powders due to the relatively low cost and availability of raw materials, as well as the active modifier action is currently tonnage used by different component matrices.

Known composition to obtain a sealing coating containing a polymer matrix and dispersed filler, which used the powder natural silicates, crushed to a size of 50-100 μm, when the content in the matrix of 0.1 to 3.0 wt.% (RF patent for the invention №2275404). A coating of this composition is applied by fluidized bed method. According to this method, cleansed and fat metal surface heated to a temperature of 30-50°exceeding the melting temperature of the matrix polymer, dip into the composite layer of powdered material placed in suspension, can withstand a specified time for the deposition of the layer of material of the required thickness, then remove from the work area setup and stand in the air until complete melting of the polymer material and forming a continuous defect-free item is offset. This technology is described in the monograph of Dovgalo VA, Yurkevich O.R. Composite materials and coatings based on dispersed polymer. - Minsk: Science and technology. - 1992. - s.

Among the disadvantages of this method is the separation of components with different mass due to the different specific gravity with the same geometric dimensions, resulting in an inhomogeneous coatings. In addition, to ensure the required level of adhesion of the coating to the substrate must be processed by a special primer (sublayer), which is an expensive and environmentally unsafe product, or phosphotyrosine. This method does not allow to apply a coating to products of large geometric dimensions, mass and complex configuration.

It is known that low-dimensional fillers and modifiers with a particle size less than 100 nm have significantly higher activity compared to particles of the same composition with a dimension of more than 1 μm (Pomogailo ROAD, Rosenberg, A.S., upland I.E. Nanoparticles of metals in polymers. - M.: Chemistry. - 2000. - 672 C.). Traditionally in polymer science applied fillers with a particle size of from 5 to 200 microns.

A method of obtaining low-dimensional fillers of natural layered minerals for polymeric materials (RF patent for the invention №2269554). The essential substance of the TB method is the treatment of the particles of the layered silicate type clay minerals and micas in thermal shock, which causes the destruction of the crystal lattice as a result of dehydration. In this way we obtain a low-dimensional particle size of not more than 100 nm, which according to modern classification referred to as nanoparticles.

The disadvantage of this method of obtaining low-dimensional particles is in need of special operations heat treatment, which is repeated several times to ensure particle size distribution of the modifier.

A known method of producing metal polymers by decomposition of metal-containing precursors (formate, oxalate, CARBONYLS, etc. in the environment of a polymer melt at a temperature of thermolysis (Pomogailo ROAD, Rosenberg, A.S., upland I.E. Nanoparticles of metals in polymers. - M.: Chemistry. - 2000. - 672 C.). This method is chosen for the prototype of the invention.

Among the significant drawbacks of this method is the need to exclude contact of the formed fine particles with an oxidizing environment using the polymer melt. Thus the melting point of the polymer should be lower than the temperature of thermolysis of metal-containing precursor for the formation of the insulating polymer layer near the particle modifier. During the decomposition of the precursor according to this method of producing metal polymers is the allocation of a significant number of the qualities of gaseous substances (CO 2N2Oh, JI), which cause foaming of the polymer matrix and complicate the processing of the composite traditional process equipment, such as injection molding machines with auger plasticities.

During the formation of coatings of mechanical mixture ingredients according to the method described in vashetitilina source, using the technology of fluidized bed portion of the precursor is isolated by the polymer melt due to the simultaneous processes of deposition, thermolysis and melting. The result is a decomposition of the precursor in air that causes oxidation of the formed fine particles of metal and the loss of their largely activity.

The present invention is to develop a method of producing metal coatings with high adaptability and providing quality metal coatings on metal parts, including large geometric dimensions, mass and complex configuration.

The problem is solved in that a method of obtaining a metal coating involves mixing powdered polymer particles selected from the group comprising polyamide, polyethylene terephthalate, high density polyethylene and powder particles of the metal-containing precursor, the representation is shining a formate or oxalate copper, Nickel, zinc, or Carbonia iron, the deposition of the mixture on the surface of the part, the heating and melting of the polymer particles, conducting thermolysis of the precursor and monolithically coating, and the heat melting the polymer particles and thermolysis of the precursor takes place simultaneously in the heat of the gas stream with a density of 3·106÷9·106W/m2for 10-4÷10-3with, the precipitation mixture and monolithically coating is produced on a workpiece heated to a temperature of T=Tp+5÷40°s, where Tpthe melting point of the polymer, when the pressure of the gas stream 3-5 ATM.

When forming the metal coating used the following components. As the polymer matrix used powders of polyamide 6 (PA6), produced by JSC grodnokhimvolokno, polyamide 11 (Rilsan) manufactured by ELF ATOCHEM (France), polyethylene terephthalate (PET) production of JSC "Mogilevkhimvolokno", high density polyethylene (HDPE) produced by JSC "Polymir" (Novopolotsk). Powders PA6, PET, HDPE received cryogenic grinding of pellets, cooled to liquid nitrogen temperature (-198°). The dispersion of the powder was 100-200 μm. As the metal-containing precursors used ant-(formate) and oxalic (oxalate salt of copper [Cu(NCOA)2], Cu(COO)2], Nickel [Ni(NCOA)2], zinc [Zn(HCO) 2] and carbonyl iron [Fe(CO)2] powders dispersion of not more than 5÷10 ám.

The powders of the polymer and the metal-containing precursor in predetermined proportions were mixed in the mixer type MOD-22 (the so-called "drunken barrel") in the presence of metal particles of a spherical shape. As technological equipment for metal-polymer coatings used to install TENA-P. the Working gases was propanebutane mixture and oxygen. The temperature of the gas stream (heat flux density) was regulated by changing the ratio and the feed rate of a mixture of propane-butane-oxygen". The substrate was heated gas stream to the optimal temperature of formation of the coating. The temperature of the substrate was controlled by pyrometer DH-39650-02 (USA). The coating is formed of a heat flux of a certain density, which gave a mixture of polymer and metal components. The residence time of the material components in thermal gas flow was regulated by changing the pressure of oxygen and propanebutane mixture. The density of the heat flow was calculated by the heat balance equation:

where m is the mass of particle, kg; m=4πR3ρ/3; R is the particle radius, m; ρ - density of material, kg/m3; Tabout- the initial temperature of the particles. K; TPL- temperature is the melting point of the material particles, K; Tmaxthe maximum temperature of the particle, K; Tmax=1,3Tp;1(T1) is the specific heat capacity of the material particles when heated from Taboutto Tp, J/(kg·K),2(T2) is the specific heat capacity of the material particles when heated from Tpto Tmax, J/(kg·); λ - specific heat melting particles, j/kg; F is the particle surface area, m2; ν is the particle velocity, m/s; Ix- distance to the sprayed surface; α(x) - heat transfer coefficient, W/(m2·k); Tp(x) is the temperature of the gas stream, TWith(x) is the temperature on the surface of the particle, K.

The floor of the prototype was formed from powder mixtures, which were placed in the installation with the possibility of creating a fluidized bed by passing a stream of air through the layer of composite material on a porous diaphragm. The metal piece was degreased and treated with primer Rilprim by dipping the parts in alcohol solution. The thickness of the sublayer of 3-5 µm. After drying, the substrate part was heated in a heating Cabinet type SNOL to a temperature of 270-320°to activate the substrate and immersed in a boiling layer of composite material at a given time. The exposure time was determined by the thickness of the coating. After deposition of the particles of the powder composition, the item was removed from the working volume of the installation, and then stood on the air until complete melting of the polymer particles and monolithically coverage, then the product was cooled in air to room temperature. Features formed in different ways coatings was evaluated by the adhesion strength with the substrate by the method of normal separation. The Brinell hardness and tensile strength. The compositions of composite materials in both methods were identical.

Technological modes of formation of coatings of metal-polymer compositions according to the proposed method and the prototype are listed in table 1.

Characteristics of metal-polymer coatings according to the developed method and the prototype are presented in table 2.

As follows from the data of table 1 and table 2, the claimed method of obtaining a metal coating is superior to the prototype performance, energy consumption and provides a higher utility features formed on substrates of steel 45 coverings.

The essence of the claimed method of producing metal coatings consists in the following. When getting a mixture of metal-containing precursor polymer in a high-temperature gas stream with the declared thermal density is the precursor decomposition with the formation of low-dimensional metal particles and melting of the polymer particles. Given that the particles of the original pre is the cursor is located in the surface layer of particles of polymer, a surface modified layer metallopolymer. Single particle metallopolymer transported by the gas flow to the substrate and contacting it deforms and takes lamellar (plate) form. Due to the pressure of the gas jet such a particle interacts with the surface layer of the substrate with the formation of a strong adhesive bond at the interface. Each subsequent particle metallopolymer interacts with the previous and forms a strong bond, forming a coating. Heating the substrate prior to the stated temperature promotes monolithically coating and increases the strength of the adhesive connection due to minimize thermal stresses on the boundary of the section "coating-substrate". The mechanical effect of the gas jet to form the coating contributes to its monolithically, removing gaseous defects in the cross section. The formation of highly dispersed metal particles (nanoparticles with sizes down to 10 nm) leads to the formation of a metal coating structure due to the interaction of the active sites of the nanoparticles and the polymer macromolecules. Metal structure has a higher strength and resistance to thermal-oxidative environments due to the manifestation of nanoparticles properties mecanova antioxidant. When forming the cover of to the position of similar composition method fluidized bed of the coating is significantly lower than the coatings obtained by said method. This is due to the following circumstances. First, the decomposition of the precursor, located on the surface of polymer particles, leads to the formation of metal oxides by oxidation of the resulting highly active metal particles in air. Secondly, part of the precursor is coated with a melt of the polymer matrix. Given the high viscosity of the melt, removing gaseous components formed by the decomposition of the precursor occurs only partially, and the resulting coating has a large number of gaseous inclusions that reduce the strength characteristics of the coating. In addition, intense leg in the process of formation reduces adhesive interaction at the interface of the "substrate-coating". Thus, the claimed method of obtaining a metal-polymer coatings has compared to prototype the following characteristic:

- the combination in a single manufacturing operation processes of the formation of low-dimensional metal particles, the melting point of the polymer particles, the formation of the coating and its monolithically;

preventing oxidation of metal nanoparticles formed during thermolysis of precursors, due to the non-oxidizing gas environment;

the formation of spatial steel structure the market over the whole cross section of the coating, providing increased strength and resistance to thermal-oxidative environments.

Advantages of the claimed method of producing metal coatings are implemented in compliance with the declared parameters of the process. The decrease in density of the heat flow below the stated limits (option IIand) or excess (option IIb), the decrease of the substrate temperature (option IIandor increase over the stated value (option IIbreduce the indicators of the performance characteristics of the coating.

A metal coating formed by the claimed method were used for the manufacture of parts of motor units at JSC "BelCard", processing metal supports of power transmission lines, as well as corrosion protection transport piping hot water and demonstrated its high reliability and efficiency.

A method of obtaining a metal coating, which consists in the fact that mixed powder of polymer particles selected from the group comprising polyamide, polyethylene terephthalate, high density polyethylene and powder particles of the metal-containing precursor, representing formate or oxalate copper, Nickel, zinc, or carbonyl iron, precipitated mixture on the surface of the part is heated, upravlyaut of Polym rye particles, spend thermolysis of the precursor and monolithically coating, and the heat melting the polymer particles and thermolysis of the precursor takes place simultaneously in the heat of the gas stream with a density of 3·106-9·106W/m2for 10-4-10-3with, the precipitation mixture and monolithically coating is produced on a workpiece heated to a temperature of T=Tp+5÷40°s, where Tpthe melting point of the polymer, when the pressure of the gas stream 3-5 ATM.



 

Same patents:

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FIELD: mechanical engineering; devices and methods for deposition of the gas-dynamic coatings.

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FIELD: chemical industry; printing industry; powder metallurgy industry; cosmetic industry; other industries; production and application of the highly anticorrosive metallic pigments.

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40 cl, 9 ex, 4 tbl, 8 dwg

FIELD: priming compositions for protection of metal surfaces working under atmospheric conditions against corrosion; application of primers and coats.

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2 tbl, 16 ex

FIELD: protective materials.

SUBSTANCE: invention relates to compositions used for applying covers. Composition contains zinc and water glass - potassium water glass as a binding agent with silicate modulus 4.8-5.3 or mixture of sodium-lithium water glass with silicate modulus 3.8-4.2 comprising the following components: soluble sodium silicate, technical lithium hydroxide, fumed silica, drinking water and ferrophosphorus. Invention can be used for protection of ferrous metals against corrosion with zinc-filled compositions. Invention provides improving anticorrosive and antifriction properties, enhancing wear resistance, electric conductivity, durability against cracking in drying, enhanced adhesion to metal, welding capacity, strength at impact.

EFFECT: improved and valuable technical properties of composition.

1 tbl

FIELD: protective coatings.

SUBSTANCE: invention relates to undercoat for metallic substrates designed for manufacturing articles and for applying top coating layers. Undercoat comprises silicate binder containing aqueous silica sol having SiO2/M2O molar ratio at least 25:1, wherein M represents sum of alkali metal ions and ammonium ion, silica particles having average size above 10 nm. Binder may further contain insignificant amount of alkali metal silicate. Content of solids in undercoat ranges between 20 and 40% (v/v) and volume ratio of pigment concentration to critic concentration thereof is below 1. Undercoat contains following proportions of components aqueous silicate sol as binder having SiO2/M2O molar ratio at least 25:1 and pH value between 9.5 and 11, wherein M represents sum of alkali metal ions and ammonium ion and silica particles are optionally modified with aluminum oxide and have average diameter 10-16 nm; 10-55% zinc and/or zinc alloy powder based on the weight of dry film having average particle size between 2 and 12 μm; 0-35% organic resin based on the weight of dry binder; and 0-30% organosilicon finishing material. Coating may contain zinc-free pigment(s) and filler increasing storage life time of undercoat. Method of applying undercoat onto steel substrate comprises preparing undercoat using silica sol, whose pH is adjusted to 9.5-11, and depositing undercoat onto steel substrate.

EFFECT: increased hardness and wear resistance, and enabled deposition of corrosion-resistant coating without blistering.

15 cl, 10 tbl, 14 ex

FIELD: corrosion protection.

SUBSTANCE: invention relates to anticorrosion compositions for metallic parts, in particular to utilization of MoO3 as agent enhancing anticorrosive properties of composition for anticorrosion coating based on dispersed metal, containing zinc of zinc alloy in aqueous phase (30-60% water in dispersion) and containing binding agent. Compositions for anticorrosion coating of metallic parts are disclosed containing such corrosion inhibitor (MoO3); at least one dispersed metal selected from group composed of zinc, aluminum, chromium, manganese, nickel, titanium, and alloys thereof; organic solvent; thickening agent; silane-based binder; optionally sodium, potassium, or lithium silicate; and water in amount from 30 to 60% by weight. Disclosed are also anticorrosion coating and metallic substrate with deposited anticorrosion coating prepared from above-defined composition.

EFFECT: improved resistance of composition to salt fog action.

22 cl, 2 dwg, 6 tbl, 3 ex

FIELD: protective materials.

SUBSTANCE: invention relates to a method for preparing priming coat for steel that is designated for assembly and applying upper coat. Steel in grounded with priming coat comprising a silicon dioxide-base binding substance containing silicon dioxide aqueous sol stabilized with aluminum oxide and, optionally, small amount of alkaline metal silicate. Indicated binding agent shows the mole ratio SiO2/M2O = at least 6:1 wherein M means the total amount of alkaline metal ions and ammonium ions. After drying the priming coat up to disappearance of stickiness in weal touch by a finger it is treated optionally with a solution that enhances the strength of the priming coat film.

EFFECT: improved and valuable properties of coat.

12 cl, 7 tbl, 21 ex

FIELD: corrosion protection.

SUBSTANCE: protective ground paint for painting coiled metal and electrochemical protection of bridges, power lines, and other long term-use metallic structures contains, wt %: epoxide resin 9.0-29.0, polyamide resin 3.0-9.5, pigment 23.0-36.0, zinc nanoparticle preparation 3.0-5.0, filler 13.0-23.2, and solvent - the balance. Zinc nanoparticle preparation is introduced in the form of (0.4-4)x·10-3 M solution in isooctane.

EFFECT: enhanced protective properties.

2 tbl, 4 ex

Coating composition // 2245893

FIELD: chemistry, in particular coating compositions, dyes and colorings.

SUBSTANCE: claimed composition includes resin with curing agent in combination with metal powder and stabilizing additive. More particular composition contains polyester resin or epoxy resin, 40-80 mass % of aluminum, iron, bronze, brass or copper powder with particle size of 25-250 mum, and as stabilizing additives at most 5 mass % of feltproofing additive and at most 20 mass % of thixotropic additive. Composition has high storage stability and useful for coating of any geometry surface.

EFFECT: coatings of high heat conductivity and thickness applicable for mechanical operation.

1 tbl

Coating composition // 2245893

FIELD: chemistry, in particular coating compositions, dyes and colorings.

SUBSTANCE: claimed composition includes resin with curing agent in combination with metal powder and stabilizing additive. More particular composition contains polyester resin or epoxy resin, 40-80 mass % of aluminum, iron, bronze, brass or copper powder with particle size of 25-250 mum, and as stabilizing additives at most 5 mass % of feltproofing additive and at most 20 mass % of thixotropic additive. Composition has high storage stability and useful for coating of any geometry surface.

EFFECT: coatings of high heat conductivity and thickness applicable for mechanical operation.

1 tbl

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