WO2009057054A2 - Procédé d'application de revêtements de phosphate sur des surfaces d'objets - Google Patents

Procédé d'application de revêtements de phosphate sur des surfaces d'objets Download PDF

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Publication number
WO2009057054A2
WO2009057054A2 PCT/IB2008/054490 IB2008054490W WO2009057054A2 WO 2009057054 A2 WO2009057054 A2 WO 2009057054A2 IB 2008054490 W IB2008054490 W IB 2008054490W WO 2009057054 A2 WO2009057054 A2 WO 2009057054A2
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WO
WIPO (PCT)
Prior art keywords
applying
layer
phosphate coating
drying
density value
Prior art date
Application number
PCT/IB2008/054490
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English (en)
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WO2009057054A3 (fr
Inventor
Avraham Sheinkman
Itzhac Rosentul
Ilana Dyskin
Vadim Kirshenbaum
Original Assignee
Greenkote (Israel) Ltd.
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Application filed by Greenkote (Israel) Ltd. filed Critical Greenkote (Israel) Ltd.
Publication of WO2009057054A2 publication Critical patent/WO2009057054A2/fr
Publication of WO2009057054A3 publication Critical patent/WO2009057054A3/fr

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Classifications

    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • 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
    • C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
    • 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
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof

Definitions

  • the present invention relates to methods of deposing powdered materials, such as paints, glues, metals, etc., on surfaces of metallic and non metallic objects, transforming them into a solid crystalline phosphate layer in the process of drying.
  • powdered materials such as paints, glues, metals, etc.
  • phosphate conversion crystalline coatings are widely used for corrosion protection of metallic objects. Thus, for example, they protect iron-based materials during neutral salt spray tests (according to ASTM Bl 17 standard) for 12-24 hrs until the base material corrosion begins. These coatings improve the corrosion protection when they are impregnated with oils, which usually contain inhibitors. In these cases, the iron-based materials start to corrode after approximately 80-100 hrs.
  • powdered phosphate conversion crystalline coatings have excellent adhesion abilities, they are also widely used in the prior art as excellent bases for many organic paints, coatings, glues, soldering and brazing materials etc. It should be noted that when compared to liquid organic and inorganic materials used for coating metallic objects, powdered materials have some very important advantages of convenience, as well as safety, in transportation and storage as a result of their reduced volume and the absence of dangerous evaporating solvents. Generally, the main technological operation in using powdered materials is a uniform deposition of the powdered components on the surface to be coated.
  • the most popular prior art methods are electrostatic powder deposition, and thermal powder grains fixation, where powder grains are blasted or pulverized on preliminarily heated objects, melted and fixed.
  • the first method usually provides a coating layer having the thickness of about 40 ⁇ m to lOO ⁇ m, while the second method provides a coating layer of about 150 ⁇ m to 1500 ⁇ m.
  • a method of applying a multilayered coating to a metal substrate that include the steps of: applying a zinc phosphating solution to a portion of the substrate, which converts the surface to a zone of an insoluble crystalline phosphate, rinsing the zone, and auto-depositing a layer of a polymer resin thereupon.
  • the present invention is a method of applying phosphate coatings to metallic and non-metallic object surfaces, by deposing powdered materials using adhesive phosphate solutions layers, which are transformed into a solid crystalline phosphate layer in the process of drying.
  • a method of applying a phosphate coating to a surface of a metallic object immediately after phosphating in a zinc phosphating solution wherein the metallic object is stili therein the solution vessel.
  • the method comprises the steps of: (a) taking the metallic object out of the zinc phosphating solution vessel, leaving the surface of the metallic object completely covered with a wet layer of the zinc phosphating solution having a density of a first density value; (b) desiccating the wet layer, the desiccating transforms the wet layer into an adhesive layer by increasing the density from the first density value to a second density value; (c) disposing at least one layer of powdered materials onto the adhesive layer, the powdered materials adhere to the adhesive layer forming a completely covered layer; and (d) drying the completely covered layer, creating an insoluble crystalline phosphate layer.
  • a method of applying a phosphate coating to a surface of a metallic object comprising the steps of: (a) applying a zinc phosphating solution to at least a portion of the surface of the metallic object.
  • the zinc phosphating solution completely covers the surface with a wet layer of the solution.
  • the phosphating solution has a density of a first density value; (b) desiccating the wet layer, the desiccating transforms the wet layer into an adhesive layer by increasing the density from the first density value to a second density value; (c) disposing at least one layer of powdered materials onto the adhesive layer, the powdered materials adhere to the adhesive layer forming a completely covered layer; and (d) drying the completely covered layer, creating an insoluble crystalline phosphate layer.
  • a method applying a phosphate coating to a surface of a non- metallic object comprising the steps of: (a) applying a zinc phosphating solution to at least a portion of the surface of the non-metallic object, the zinc phosphating solution completely covers the surface with a wet layer of the solution, the phosphating solution having a density of a first density value; (b) desiccating the wet layer, thus transforming the wet layer into an adhesive layer by increasing the density from the first density value to a second density value; (c) disposing at least one layer of powdered materials onto the adhesive layer.
  • the method further comprises the step of: (e) curing the completely covered layer.
  • the first density value is between 1.00 kg/1 and 1.20 kg/1. According to yet another feature of the present invention, the first density value is between 1.03 kg/1 and 1.15 kg/1.
  • the first density value is between 1.03 kg/1 and 1.10 kg/1.
  • the second density value is larger than 1.25 kg/1.
  • the second density value is between 1.25 kg/1 and 1.50 kg/1. According to yet another feature of the present invention, the second density value is larger than 1.25 kg/1.
  • the second density value is between 1.25 kg/1 and 1.50 kg/1.
  • the desiccating means reducing the volume of said wet layer 4 to 5 times.
  • the desiccating is selected from a list of means including: heating with infrared radiation, air drying, sublimation, vacuum drying, microwave drying and ultrasonic drying,
  • the powdered materials include additives for acquiring required attributes. These additives are selected from a listing including: paints, sealers, glues, coatings materials, dry lubricants, and pigments. According to still another feature described in the preferred embodiments, the powdered materials include materials selected from a list of metallic powders. These metallic powders include zinc, zinc oxide, calcium, salts, iron, iron oxide, iron salts, and manganese salts.
  • the drying of the completely covered layer is accomplished above 40 0 C.
  • the curing is 5 done above 15O 0 C.
  • the curing is done between 15O 0 C and 225 0 C. According to yet another feature of the present invention, the curing is done between 180 0 C and 200 0 C 5 and
  • the non-metallic object is a wooden object.
  • the present invention successfully addresses the shortcomings of the existing technologies by providing a method of applying a phosphate 1.5 coating to a surface of a metallic object immediately after phosphating in a zinc phosphating solution, without any intermediate washing.
  • This method is also method of applying a phosphate coating to a surface of a metallic, as well as a non-metallic object.
  • the present invention is simple, reliable and inexpensive, and provides thin and homogeneous coating to the treated object.
  • the present invention is a method of applying phosphate coatings to metallic and non-metallic object surfaces, by deposing powdered materials using adhesive phosphate solutions layers, which are transformed into a solid crystalline phosphate layer in the process of drying.
  • phosphate solutions of divalent and trivalent metals are adhesive. However, they are very unstable and easily crystallize at a density equal to, or greater than 1.25 kg/I. Therefore, phosphate solutions with the density of 1.03 kg/1 to 1.10 kg/1 are usually used in industry. These solutions are stable enough, but have no adhesive properties, because their molecules in this density-range are mainly in the monomolecular form.
  • the thin liquid phosphate solution layer which remains on the treated surface, is usually removed by repeated rinsing in water or neutralization solutions. After rinsing, the objects are dried, and finally a solid crystalline layer of phosphates covers the surface of the treated objects.
  • the divalent and trivalent metals applied for the phosphating process are phosphates of zinc, iron, calcium, manganese as well as their combinations.
  • the surface of objects to be treated is phosphatized with non-adhesive phosphate solutions, having the density of 1.00 kg/1 to 1.20 kg/1, preferably 1.03 kg/1 to 1.15 kg/1, and more preferably 1.03 kg/1 to 1.10 kg/1
  • these objects are small metallic parts, which are very frequent in the machinery and vehicle industries.
  • the treated objects are desiccated instead of being rinsed. Consequently, the density of the thin phosphate solution layer, which remains on the treated surface, is increased to, or above 1.25 kg/1 and thus becomes adhesive.
  • the powdered materials are deposited onto this adhesive phosphate solution layer, and adhere thereon it. If desired the process may be repeated to produce a multilayer coating on the surface of the treated objects. After getting the desired coating thickness, the coating is dried, and, if needed, cured.
  • the innovative coating structure includes three combined layers: a crystalline phosphate conversion layer produced in the process of phosphalmg, an intermediate crystalline phosphate layer produced at the crystallization of the adhesive phosphate layer during the desiccations stage, layer of paint, glue coating, etc. produced from the powdered materials, which include suitable additives, during the drying and curing stages.
  • preliminarily phosphated dry objects and objects that cannot be phosphatized are wetted by a phosphating solution, and then the treatment continues in the above- described method: desiccating the treated objects and depositing powdered materials, drying and curing.
  • the main important requirement of the method is the formation of an adhesive layer of phosphate solution on the objects surfaces by desiccation. It should be stressed that this particular embodiment is suitable to treat non-metallic objects such as wood or plastic.
  • the phosphating liquid should be completely removed after the phosphating process by rinsing with water, while in the present invention the remaining phosphating solution is turned into an adhesive solution by desiccating to a density of at least 1.25 kg/1.
  • the water content of the phosphate salts solution on the surface of the treated objects is reduced so as to obtain a density larger than 1.25 kg/1 , and preferably of 1.25 kg/1 to 1.5 kg/1, at which the phosphate salts solution acquires adhesive properties.
  • the water content of the initial phosphaling liquid is reduced 4 to 5 times.
  • This effect may be attained by controlled desiccation of the initial solution using any known industrial method such as heating the surface of the treated objects with infrared radiation, air drying, sublimation, vacuum drying, microwave drying, ultrasonic drying, etc.
  • the desiccation method chosen for any specific case is the most suitable and most economical one for the case.
  • powdered materials such as paints, sealers, glues, coatings materials, dry lubricants, pigments, etc. are dispersed on the surface.
  • the liquid adsorption layer should be crystallized into a water-insoluble phosphate salt, usually Zn 3 (PO 4 ) 2 '4H 2 O.
  • the phosphating solution contains excessive amount of phosphoric acid, which should be bound into a solid insoluble salt. It should be reminded that only phosphates of bivalent and trivalent metals are water-insoluble.
  • the present innovative method may be combined with processes of powder materials melting or powder materials curing above 150 0 C, preferably between 150 0 C, and 225 0 C and most preferably between 180 0 C and 200 0 C .
  • Zinc phosphate was chosen as a base material for the solutions that were used for zinc-phosphating of steel objects as well as steel objects after sherardizing process, which is a diffusion coating of steel with zinc.
  • Different phosphating solutions having the densities of 1.03 kg/1, 1.09 kg/1 and 1.2 kg/1 were prepared by diluting the PSC with tap water.
  • the main process equipment used in carrying the experiments was: • A drying box, Thermoplus, manufactured by Dahan Technologies Ltd;
  • a plastic drum having a volume of 1 liter, and a diameter of 70 mm;
  • the processed samples used in experiments 1 to 8 were sherardized steel plates of 40x40x3 mm made of low carbon steel SAE 1020.
  • the thickness of the sherardizing coating layer, in these experiments, was 40 ⁇ 5 ⁇ m.
  • experiment 9 the same steel plates without coating were tested, while in experiment 10, 40x40X6 mm oak-wood plates were used.
  • Sherardized samples for experiments 1 to 8 were initially phosphated, according to the conventional process, in a laboratory plastic beaker having the volume of 0.5 liter. The temperature of the phosphating liquid was 35° ⁇ 2°C, and the duration of the phospatizing step was 10 minutes. 2. After phosphating, the samples were rinsed, thoroughly dried and weighed. 3. The phosphated samples were immersed in phosphating solutions with different initial densities and weighed again.
  • the samples were covered with a homogenized powdered mixture, including a black polyester powdered paint, produced by DuPont Company, France, and 5% of zinc oxide powder. This was performed in a regular flu ⁇ dized-bed chamber, where the powder grains adhere to the sticky high-density desiccated phosphating liquid layer on the surface of the samples.
  • the samples were cured in the drying box at a temperature of 180 0 C to 200 0 C for 10 minutes.
  • the pH value of an aqueous extract after the thermal treatment of these coated samples was 7 to 8.
  • IL d m / (s* p) where: mo is the initial mass of the layer in g; m is the mass of the same layer after desiccation in g;
  • ⁇ m is equal to (m 0 - m) in g;
  • Po is the density of the initial phosphating solution in g/cm 3
  • p H2 ⁇ is the density of water in g/cm 3
  • s is the area of the sample in cm 2 .
  • non-metallic objects such as objects made of wood.
  • This novel method enables to prepare an adhesive layer of aqueous

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention porte sur un procédé d'application d'un revêtement de phosphate sur une surface d'un objet métallique immédiatement après la phosphatation dans une solution de phosphatation au zinc, l'objet métallique étant encore dans le récipient de solution. Le procédé consiste : (a) à retirer l'objet métallique du récipient de solution de phosphatation au zinc, laissant la surface de l'objet métallique complètement recouverte d'une couche humide de la solution de phosphatation au zinc, la solution de phosphatation ayant une densité égale à une première valeur de densité ; (b) à sécher la couche humide, le séchage transformant la couche humide en une couche adhésive par l'augmentation de la densité de la première valeur de densité à une seconde valeur de densité ; (c) à disposer au moins une couche de matières pulvérulentes sur ladite couche adhésive, les matières pulvérulentes adhérant à la couche adhésive pour former une couche complètement recouverte ; et (d) à sécher la couche complètement recouverte, le séchage créant une couche de phosphate cristallin insoluble.
PCT/IB2008/054490 2007-10-31 2008-10-29 Procédé d'application de revêtements de phosphate sur des surfaces d'objets WO2009057054A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US98395807P 2007-10-31 2007-10-31
US60/983,958 2007-10-31

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WO2009057054A3 WO2009057054A3 (fr) 2009-12-23

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Cited By (5)

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WO2016003601A1 (fr) * 2014-07-01 2016-01-07 Heat Technologies, Inc. Système et procédé de séchage acoustique indirect
WO2017077514A1 (fr) * 2015-11-05 2017-05-11 Phosfan Ltd. Revêtements composites au phosphate
US9671166B2 (en) 2014-07-24 2017-06-06 Heat Technologies, Inc. Acoustic-assisted heat and mass transfer device
US10006704B2 (en) 2009-02-09 2018-06-26 Heat Technologies, Inc. Ultrasonic drying system and method
US11142828B2 (en) 2015-05-07 2021-10-12 Phosfan Ltd. Method for applying ultrafine phosphate conversion crystal coatings

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5455075A (en) * 1994-03-10 1995-10-03 Daubert Chemical Company, Inc. Hot melt corrosion inhibiting coating composition
US6235407B1 (en) * 1997-04-09 2001-05-22 Kawasaki Steel Corporation Steel plate for highly corrosion-resistant fuel tank
US6432491B1 (en) * 1999-03-25 2002-08-13 E. I. Du Pont De Nemours And Company Method for producing multi-layer paint coatings
US20040009300A1 (en) * 2000-10-11 2004-01-15 Toshiaki Shimakura Method for pretreating and subsequently coating metallic surfaces with paint-type coating prior to forming and use og sybstrates coated in this way
US20020102356A1 (en) * 2000-11-22 2002-08-01 Agarwal Rajat K. Protective reaction rinse for autodeposition coatings
US20020102407A1 (en) * 2000-12-06 2002-08-01 Josef Huybrechts Aqueous coating compositions with phosphonic acid based compounds
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US20070125644A1 (en) * 2005-09-15 2007-06-07 Board Of Regents, The University Of Texas System Reduction of the loss of zinc by its reaction with oxygen in galvanized steel and batteries

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11353263B2 (en) 2009-02-09 2022-06-07 Heat Technologies, Inc. Ultrasonic drying system and method
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US10775104B2 (en) 2009-02-09 2020-09-15 Heat Technologies, Inc. Ultrasonic drying system and method
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