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WO2006006141A1 - Procede d'application de revetement cristallin par conversion zinc-phosphate - Google Patents

Procede d'application de revetement cristallin par conversion zinc-phosphate Download PDF

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Publication number
WO2006006141A1
WO2006006141A1 PCT/IL2004/000631 IL2004000631W WO2006006141A1 WO 2006006141 A1 WO2006006141 A1 WO 2006006141A1 IL 2004000631 W IL2004000631 W IL 2004000631W WO 2006006141 A1 WO2006006141 A1 WO 2006006141A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
phosphate
filler particles
phosphating
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IL2004/000631
Other languages
English (en)
Inventor
Avraham Sheinkman
Yitzchak Rosenthul
Ilana Dyskin
Zvi Mendelsohn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Greenkote (Israel) Ltd
Original Assignee
Greenkote (Israel) Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Greenkote (Israel) Ltd filed Critical Greenkote (Israel) Ltd
Priority to PCT/IL2004/000631 priority Critical patent/WO2006006141A1/fr
Priority to US11/572,137 priority patent/US20100132845A1/en
Publication of WO2006006141A1 publication Critical patent/WO2006006141A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
    • 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
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C04B2111/00525—Coating or impregnation materials for metallic surfaces
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to a method of applying phosphate conversion coating, and specifically zinc-phosphate conversion crystal coating (ZPCCC), on steel, cast iron, various metals and alloys, and on different types of Zinc coatings on metals.
  • ZPCCC zinc-phosphate conversion crystal coating
  • Phosphate conversion coating and specifically zinc-phosphate conversion crystal coating, is used for improving paint coatings, rubber coatings, organic, and inorganic coatings to metal surfaces.
  • zinc-phosphate coating is applied to increase corrosion protection for metals, where the coating works as a carrier for the specific oil or wax film that is applied over it.
  • Zinc phosphate is a crystalline conversion coating that is formed on a metal substrate, utilizing the chemical reaction between metal ions that have been dissolved in mineral acids and then diluted with water to form the process solution.
  • the mineral acids that are normally used to dissolve the metal ions are nitric acid and phosphoric acid.
  • Metals such as Zinc, Nickel and Manganese are dissolved depending on the process necessary. Accelerators may be added to phosphating processes to increase reaction speed, modify hydrogen elimination and control sludge formation.
  • the first reaction that occurs when the zinc phosphate solution comes into contact with the metal surface is the pickling reaction, in which some metal is dissolved from the surface.
  • a chemical cleaning of the surface takes place. This cleaning affects the adhesion of the coating to the base metal.
  • the free acid of the solution close to the metal surface is consumed because of the dissolution of the metal surface.
  • Metal ions are transferred into the process solution.
  • the type of metal depends on the type of substrate mix being treated.
  • the second reaction is the coating reaction. Due to free acid consumption in the liquid-metal interface, pH rises and the metal cations can't stay soluble in the solution. They react with the phosphate in the solution and deposit on the metal surface as crystalline Zinc Phosphate.
  • the third reaction is the sludge formation reaction.
  • the metal ion (Fe++) that is dissolved from the pickling reaction is oxidized using the accelerator and will precipitate out as sludge.
  • the sludge, created in the process, is normally filtered out from the solution utilizing some sort of filter media or equipment.
  • Zinc Phosphating Several different processes can be utilized with Zinc Phosphating. Straight spray installations are popular, as well as straight dip operations. Because the spray utilizes the kinetic energy of the spray pressure, concentrations and treatment times can be kept lower in spray operations compared to dip. Heavy Zinc Phosphating processes are applied in dip operations, either in bulk processes utilizing tumblers, or in a specific rack design.”
  • the parts, or substrates, to be coated are immersed in a solution that contains soluble zinc-phosphates (or soluble phosphates of iron, nickel, or manganese).
  • the solution reacts with a base metal, and as result an insoluble layer of phosphate crystals is created on the part's surface.
  • the rate of reaction of this process, and the properties of the created layer depend on: the concentrations of the free and bonded Phosphoric Acid; the concentration of the metal ions; the temperature and the acidity of the solution.
  • the coating application processes are similar for the various types of phosphate solutions. Relatively small substrates are loaded into special immersion baskets, or rotated drums, and immersed in the phosphate solution baths. They are immersed for a set dwelling time, and then transferred to rinsing baths. (Several baths, containing different solutions are sometimes required.) The coated parts/substrates are then dried. Large substrates may often be immersed as they are.
  • Another popular phosphate coating method is spraying the parts, with a spray solution taken from the phosphate solution tank, to coat them.
  • a spray solution taken from the phosphate solution tank
  • the coating process problems include the following:
  • the phosphate coating rate and phosphate crystals size depend, both, on solution composition and the surface condition of the substrate. For example, grinding or polishing the substrate surface results in small phosphate coating crystals. Small size phosphate coating provides better corrosion resistance and paint adhesion.
  • phosphate coating crystal size stability is an additional phosphate coating process problem.
  • Special activators such as Titanium Phosphate, are used to help create phosphate coating with specific crystals size.
  • the activator stability and its lifetime in the phosphate solution depend on several parameters, including: acidity, salt concentrations, temperature, and surface roughness.
  • the ZPCCC mechanism is described in the article by John Donofrio (see above).
  • the main principle of this process is that the zinc-phosphate solution reactions take place in a thin layer above the metal surface.
  • the solution reacts with the metal.
  • the acidity in this thin layer diminishes.
  • the solution is shifted from its equilibrium state, and consequently, an insoluble crystal layer is formed on the metal surface.
  • the bath solution is constantly agitated. As a result, the solution, situated in the thin layer above the metal surface, is constantly renewed. Solution that has undergone reaction is mixed in with the bulk bath solution. This solution transfer process decreases the coating formation rate. It also disturbs the equilibrium of the bulk bath solution, resulting in the precipitation of insoluble phosphates in the bath solution, and its contamination. Thick ZPCCC layer creation requires increasing the temperature and adding special activators, which in turn increase the bath solution contamination rate.
  • This method increases the bath solution lifetime and the ZPCCC process stability.
  • the reactor volume must be large enough to maintain a stable process.
  • the real, bulk density of steel items is usually 1-4 kg/L. Since the steel density is 7.8 kg/L, the unfilled volume of the bulk volume is, on the average, 0.7 L/kg. To provide ZPCCC process uniformity, all this volume should be filled with solution. Therefore, for a 200 kg batch of substrate, the minimal reactor volume should be 140 L, and in real industrial situations a volume of 500 L. is reasonable. Therefore, the volume of solution, required for the process, is a hundred times more than the volume of solution, actually required for ZPCCC formation. For example:
  • phosphate salt concentration in bath solution is 100 g/L. Therefore, 500 L of solution contain 50,000 g phosphate salts, which is 600 times more than was needed for the ZPCCC formation.
  • the preferred embodiment of the present invention deals with corrosion resistance phosphate coatings that require 10 g/m2 and more.
  • a process reactor volume containing a quantity of relatively small, chemical inert filler particles.
  • the shape and size of these filler particles may be varied according to the application.
  • the particle size ranges between 1 to 20 mm (usually 2-5 mm).
  • the quantity of phosphate solution, required for the modified ZPCCC process depends on the filler's solution absorption ability.
  • the modified ZPCCC process is performed, using either continuous or periodic movement of treated parts and filler particles, continually exposing substrate surfaces to fresh solution.
  • This method is herein described as Absorbed Solution Layer Phosphating (ASLP).
  • the required filler volume should be 140 L., and the filler particles are present as spheres having a 3 mm diameter.
  • the phosphate solution volume, absorbed on this quantity of filler is approximately 3-5 L.
  • This volume of phosphate liquid contains enough phosphate salts for providing the required thickness of ZPCCC.
  • the ZPCCC reaction is carried out in a small volume of solution, in an interface layer between the treated substrate and the filler particle. The solution reacts rapidly not only on the border between the solution and the substrate, but also in all the interface layer volume. During the period of time when there is movement of treated parts relative to filler particles , fresh phosphate solution is introduced to the interface layer, enabling rapid coating layer creation and uniform coating thickness.
  • a thick, uniform ZPCCC layer may be created without having to add any special activators.
  • ASLP is carried out in a reactor, which provides either continuous or periodic movement of treated parts and filler particles.
  • the simplest types of reactors use a drum rotated at a speed of 0.2 - 1 r.p.m., or a vibrating machine.
  • Other mixing options involve using the magnetic properties of treated substrates being passed through the filler.
  • Units for reactor loading and reloading, and for phosphate solution addition and removal/exchange are generally required.
  • Fig. 1 shows the ASLP batch process diagram
  • Option 1 Heated phosphating solution is provided from tank 1 to the ASLP reactor 2, which is already filled with the required amount of filler particles, during the time required for filler heating and rinsing.
  • the solution, used for rinsing is removed from the ASLP reactor 2 to the cleaning system 4, by gravitation or by pumping. Cleaning is performed using a filter, precipitator, or hydro-cyclone.
  • the treated solution is returned to tank 1, as required.
  • valve A Before phosphating, valve A is turned off and all the solution from the reactor is removed, except for the solution absorbed on the filler particle surfaces.
  • a batch of the substrate, to be treated is loaded and treated for the period of time required to attain the required thickness of ZPCCC. During the ASLP process, periodic or continuous movement of the treated parts and filler particles is carried out.
  • the coated substrate may be rinsed in the reactor, or transferred for required finishing, for example, rinsing, neutralizing etc., to other equipment. Finally, the coated substrate undergoes a drying operation.
  • Tank 1 contains heated washing liquid for substrate washing, before and after phosphating. After the washing liquid is removed from reactor 2 to the tank, as in the previous process option, valve A is turned off, and a small quantity of phosphating solution concentrate is added to the reactor 2. This concentrate is mixed with a washing solution, which was absorbed on the filler particles' surface. The quantity of phosphating solution concentrate is calculated, so that the final composition of solution absorbed on the filler particles is that required for the phosphating process. The batch of substrate, to be treated, is loaded into the reactor and the process continues as in the previous process option.
  • the density of the CPS liquid was increased to 1.300 g/cm 3 by adding water.
  • Phosphating solutions were prepared by mixing CPS with water or washing solution
  • Washing solution was prepared by mixing CPS with water to obtain a density of 1.040 g/cm 3 ; the pH of this solution was 2.80.
  • ZnO pigment grade, producer - "Numinor Ltd.”
  • H 3 PO 4 technical grade, density 1.65 g/cm 3 , supplier - "Chemilab Ltd.”
  • Acidity of phosphating liquid was measured by pH-meter .
  • the method of phosphating was based on the known process of phosphating in a bath, simulated in laboratory plastic beaker, having a volume of 0.5 liter.
  • control samples were washed in running water and dried using paper towels.
  • the plates were diffusion saturated in Zinc powder at 410 0 C during 1 hour. 8.
  • the thickness of Zn-Fe layer that was received by the above- mentioned method was approximately 40 ⁇ 5 micron.
  • the phosphating solution was prepared via mixing one part of CPS and three parts of water.
  • the density of the phosphating solution was 1.090 g/cm 3 , pH was 2.48.
  • Experiment #7 Repeated Experiment #5 with the difference being that used the solution prepared for experiment #6.
  • Experiment #8 Repeated Experiment #5 with the difference being that 1 kg of corundum powder, with average grain size 850 micron, was added to the drum.
  • the vibrator was filled with 150 kg of chips (the same size used for Experiments ##2-9).
  • Phosphating solution was added to the vibrator and 50 kg of metal, including three, control samples, were added.
  • the frequency of the electrical current supplying the vibrator motor was used as an indicator of the rate of moving chips in the vibrator.
  • the phosphated articles were un-loaded at a frequency of 30 Hz, during 5 minutes.
  • the washing solution was pumped into the bath with a device for sludge settling.
  • Experiment #13 Repeated Experiment #12 with the difference being that the phosphating time was 15 minutes.
  • Experiment #14 Repeated Experiment #12 with the difference being that the phosphating time was 7 minutes.
  • Experiment #15 Repeated Experiment #12 with the difference being that 1.5 -liter of
  • the ASLP process performs consistently in a wide range of varying phosphating solution compositions (Experiments # 7, 9, 10, 11, 12, 16, 17, 19), varying phosphating time (Experiments # 10, 13, 14), varying filling grains size (Experiments # 2, 8, 10, 20), varying speeds of substrate and filler movement (Experiments # 2, 3, 5, 10).
  • the process without adding activators, obtains a very good thickness of phosphate layer (up to 15 g/cm 2 ), small sizes of crystals (1 micron and less) and high corrosion stability (336 hours in SST).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention concerne un procédé d'application de revêtement par conversion zinc-phosphate modifié, appelé procédé de revêtement ASLP (Absorbed Solution Layer Phosphating). Ce procédé d'application de revêtement cristallin par conversion zinc-phosphate modifié (ZPCCC) est appliqué dans un réacteur qui contient un substrat métallique, une certaine quantité de solution phosphatée et une certaine quantité de particules de charge solides inertes, la quantité de solution phosphatée dépendant de la capacité d'absorption de solution des particules de charge solides. Le procédé ASLP est exécuté dans une couche d'interface entre le substrat et les particules de charge solides. Le réacteur étant conçu pour imprimer un mouvement réciproque aux pièces traitées et aux particules de charge, de manière à exposer en continu les surfaces du substrat à une solution phosphatée fraîche.
PCT/IL2004/000631 2004-07-14 2004-07-14 Procede d'application de revetement cristallin par conversion zinc-phosphate Ceased WO2006006141A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/IL2004/000631 WO2006006141A1 (fr) 2004-07-14 2004-07-14 Procede d'application de revetement cristallin par conversion zinc-phosphate
US11/572,137 US20100132845A1 (en) 2004-07-14 2004-07-14 Method of applying zinc-phosphate conversion crystal coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IL2004/000631 WO2006006141A1 (fr) 2004-07-14 2004-07-14 Procede d'application de revetement cristallin par conversion zinc-phosphate

Publications (1)

Publication Number Publication Date
WO2006006141A1 true WO2006006141A1 (fr) 2006-01-19

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3847951A (en) * 1972-02-28 1974-11-12 Chevron Res Insecticidal n-thio-substituted carbamates of dihydrobenzofuranols
US5399208A (en) * 1989-12-19 1995-03-21 Nippon Paint Co., Ltd. Method for phosphating metal surface with zinc phosphate

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2254378A1 (de) * 1972-11-07 1974-05-22 Metallgesellschaft Ag Verfahren zur vorbehandlung von massenteilen fuer die spanlose kaltumformung
DE3800834A1 (de) * 1988-01-14 1989-07-27 Henkel Kgaa Verfahren und mittel zum gleichzeitigen gleitschleifen, reinigen und passivieren metallischer werkstuecke
US5117370A (en) * 1988-12-22 1992-05-26 Ford Motor Company Detection system for chemical analysis of zinc phosphate coating solutions
US5140783A (en) * 1990-06-26 1992-08-25 Hoffman Steve E Method for surface finishing of articles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3847951A (en) * 1972-02-28 1974-11-12 Chevron Res Insecticidal n-thio-substituted carbamates of dihydrobenzofuranols
US5399208A (en) * 1989-12-19 1995-03-21 Nippon Paint Co., Ltd. Method for phosphating metal surface with zinc phosphate

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