WO1994012289A1 - Procede permettant de proteger une surface a l'aide de composes silicates - Google Patents

Procede permettant de proteger une surface a l'aide de composes silicates Download PDF

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Publication number
WO1994012289A1
WO1994012289A1 PCT/US1993/011279 US9311279W WO9412289A1 WO 1994012289 A1 WO1994012289 A1 WO 1994012289A1 US 9311279 W US9311279 W US 9311279W WO 9412289 A1 WO9412289 A1 WO 9412289A1
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WO
WIPO (PCT)
Prior art keywords
silicate
layer
containing solution
solution
acid
Prior art date
Application number
PCT/US1993/011279
Other languages
English (en)
Inventor
Nathan C. Crews, Iv
Daniel A. Young
Lance A. Young
Original Assignee
Dancor, Inc.
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 Dancor, Inc. filed Critical Dancor, Inc.
Priority to EP94902326A priority Critical patent/EP0701489A1/fr
Priority to RU95113589A priority patent/RU2123894C1/ru
Priority to JP6513284A priority patent/JPH08503656A/ja
Priority to BR9307502A priority patent/BR9307502A/pt
Priority to AU56733/94A priority patent/AU691794B2/en
Priority to KR1019950702049A priority patent/KR950704057A/ko
Publication of WO1994012289A1 publication Critical patent/WO1994012289A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/06—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • 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
    • C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/02—Selection of the hardening environment
    • C04B40/0263—Hardening promoted by a rise in temperature
    • 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
    • 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
    • C09D5/18—Fireproof paints including high temperature resistant 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
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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

Definitions

  • Another type of protective barrier uses silicate compounds which are chemically bonded to various metallic surfaces. It is widely known that various silicate compounds can be used to form hard, smooth surfaces that are resistant to abrasion and corrosion.
  • U.S. Patent No. 3,658,662 to Casson, et al. discloses lithographic plates made of aluminum or aluminum alloy material that are silicated to provide a hard, smooth barrier between the plate's surface and the corrosive diazonium salts and other photosensitive coatings used in the lithographic process.
  • Another advantage of silicate compounds is their heat and fire resistant properties.
  • U.S. Patent No. 4,810,741 to Kim discloses an elaborate process for producing a fire-resistant, non-combustible material containing silicate compounds. However, such silicated materials still allow unacceptably high levels of corrosion, and are prone to be dissolved by solvents.
  • One type of coating which uses silicate compounds is applied using electrolytic processes, such as that disclosed in U.S. Patent No. 3,658,662 to Casson, et al.
  • This process involves the use of a basic electrolyte solution of sodium silicate or other salts and a piece of aluminum which acts as an anode. Electricity is supplied between the aluminum anode and a cathode in order to cause an aluminum silicate barrier to form on the surface of the aluminum anode.
  • This process cannot be used on surfaces which do not conduct electricity, such as wood.
  • Some prior art protective coatings particularly coatings for metals, also contain toxic substances, such as chromates and cadmium. Such substances are both harmful to the environment and expensive to dispose of.
  • the processes for creating such coatings such as the widely used chromate conversion coating, also create other waste disposal problems.
  • the coatings created by such processes moreover, lack great resistance to abrasion. There is therefore a great need for an improved protective coating for metals and other materials that does not use substances that are toxic or otherwise harmful to the environment and that confers greater resistance to abrasion. Summary
  • the protective layer formed by the method of the present invention provides a coating for a relatively rigid surface of an article that is highly resistant to abrasion, corrosion, solvents, fire, and other destructive forces.
  • This protective layer is formed from non-toxic materials by a process which itself does not generate further hazardous waste.
  • the present invention therefore represents a significant improvement in the art of protective layers for coatings for rigid surfaces.
  • a method for treating a rigid surface of an article in order to form a protective layer on that rigid surface comprises the steps of:
  • the hydrophilic surface can be created by any of various means, including chemical means and mechanical means, such as sanding the surface.
  • the hydrophilic surface can also be rinsed before it is exposed to the silicate- containing solution.
  • the silicate-containing solution contains between 10% and 100% (by volume) of a silicate compound.
  • the silicate-containing solution contains between 20% and 40% (by volume) of the silicate compound.
  • the silicate-containing solution is also preferably a sodium silicate solution, although the silicate-containing solution can as well be a potassium silicate solution.
  • the hydrophilic surface is exposed to the silicate-containing solution, it can be exposed for between 1 and 60 seconds in order to form the layer of silicate-containing solution.
  • the hydrophilic surface is exposed to the silicate-containing solution for 20 seconds or less
  • this step comprises exposing the layer of silicate-containing solution on the hydrophilic surface to the environment having an initial temperature of between 120°F and 150°F and then raising the temperature of the environment at a rate of between about 30°F and 60°F per minute until a temperature of between 305°F and 350°F is reached.
  • the entire drying step lasts for between about 2 minutes and 50 minutes, and preferably for between 6 minutes and 15 minutes.
  • the acid used in the present method can be an acidic solution which contains between 1% and 99% by volume of an acid, although the acidic solution preferably contains between 10% and 30% by volume of the acid.
  • the acid can be phosphoric acid, which is inexpensive and readily available.
  • the dried layer of silicate material is exposed to the acidic solution for between about 5 seconds and 120 seconds, and preferably for between 20 seconds and 50 seconds.
  • acidic solution can be between 68°F and 180°F when the dried layer of silicate material is exposed to the acidic solution.
  • steps (b) to (d) above are repeated a plurality of times in order to provide improved corrosion resistance and other characteristics.
  • the protective layer is rinsed to remove excess acid.
  • Another embodiment of the present invention comprises an article having a rigid surface on which a protective layer has been formed, the protective layer being formed by:
  • a method for treating an article having a rigid surface in order to form a protective layer on the rigid surface comprises the steps of:
  • This method can additionally comprise the step of providing a hydrophilic surface on the rigid surface before applying the uniform layer of the silicate-containing solution to the rigid surface.
  • a protective layer on a rigid surface comprising: an outer layer comprising silicon dioxide, the outer layer being non-porous; and an inner layer comprising silicon dioxide and a metal oxide, the inner layer being water-soluble.
  • Figure 1 is a cross-sectional view of a metallic article having a protective layer formed thereon comprising one inner layer of silicate salt and an outer bi-layer.
  • Figure 3 is a cross-sectional view of a metallic article having a protective layer formed thereon comprising two bi- layers.
  • Figure 4 is a cross-sectional view of a wood article having a protective layer formed thereon comprising two inner layers of silicate salt and an outer bi-layer.
  • Figure 6 is a graphic illustration of one aspect of a preferred embodiment of the present method for treating rigid articles in order to form a protective layer thereon.
  • the present invention comprises an improved method of treating a rigid surface of an article in order to create a protective layer on that surface. It is believed that the surface of any relatively rigid material, such as a metal, can be treated according to the present method in order to protect the surface of that material.
  • the protective layer created by the present method is believed to contain substantial amounts of silicon dioxide, and has been found to be substantially resistant to most chemical solvents.
  • the process disclosed herein forms a protective layer comprising an outer layer of silicon dioxide over one or more inner layers of silicate salt.
  • the process begins by creating a fixed surface on an article, such as metallic or wood article.
  • the fixed surface is created by first washing the surface with detergent and hot water. With metallic articles, the surface is then exposed to a fixing acid solution which etches or chemical reacts with the surface to form a thin film layer thereon.
  • the film layer contains binding substances, such as metallic oxide material, which enables the layer of silicate salt formed in the next step to bind to the surface.
  • the fixing acid is phosphoric acid, which forms a thin film layer comprising metallic oxide and metallic ortho-phosphate material.
  • the entire process may be repeated to form a plurality of layers of silicate salt over the lower layers of silicate salt.
  • Each layer of silicate salt provides greater protection to the article against abrasion, corrosion, fire and heat.
  • a strong acid such as an acidic solution.
  • the final layer of silicate salt is transformed into an outer bi-layer structure comprising an inner layer of silicate salt and an outer layer of silicon dioxide.
  • the protective layer comprises a plurality of inner layers of silicate salt at least partially converted into silicon dioxide and an outer bi-layer comprising an inner layer of silicate salt and an outer layer of silicon dioxide.
  • each layer of silicate salt is transformed into an inner bi-layer comprising a layer of silicate salt and an outer layer of silicon dioxide.
  • one inner bi-layer is formed under the outer bi-layer to provide sufficient protection.
  • the thin film layer 16 preferably contains a binding substance, such as a metallic oxide material, which enables the layer of silicate salt formed later to bind to the surface.
  • the fixing acid solution is 20% to 25% phosphoric acid and is left on the surface for 3 to 10 minutes.
  • phosphoric acid is used as the fixing acid solution, it is postulated that it etches and chemically reacts with the surface to form a thin film layer 16 comprising metal ortho-phosphate and a metal oxide salt.
  • acids stronger than phosphoric acid such as hydrochloric acid, are used on metallic surfaces, excessive oxidation of the surface may occur.
  • the impurities generally referred to as smut material, comprise various oxides and phosphate salts
  • desmutting is conducted for appearance value only, since the smut material does not appear to hinder the creation of or the functioning of the protective layer.
  • desmutting is conducted by washing the film layer 16 with warm or hot water, 120°F-140°F. Pressure and scrubbing action as well as other desmutting methods may also be used.
  • the smut material is apparent by a dark grey to black color on aluminum alloys.
  • the metallic ortho-phosphate or metallic oxide material found in the film layer 16 chemically bonds with the sodium silicate in the solution to form the inner layer of silicate salt 18.
  • the actual exposure time to the silicate solution can vary from about 1 to 10 minutes, depending upon the type of article and surface being treated. With smooth surfaces, for example, shorter exposure time is required than with rough or pitted surfaces. Also, some materials require longer exposure times than others. For example, surfaces made of aluminum or aluminum alloys require a shorter exposure time than magnesium or magnesium alloy surfaces.
  • the drying step is carried out in an oven at 302°F or more. At this temperature, complete drying takes between about 2 and 30 minutes. It has been discovered that when sodium silicate is dried at 302°F or more, a portion of it is converted into silicon dioxide, which appears to increase the resistance of the inner layer 18 to abrasion and corrosion. By increasing or decreasing the temperature or the drying time, the amount of conversion of sodium silicate into silicon dioxide can be increased or decreased, respectively, to create layers having different abrasion and corrosion-resistant properties.
  • the inner layer 18 After the inner layer 18 has dried completely, it is then preferably exposed again to the 18-33% (v/v) sodium silicate solution for about one to three minutes and then dried in the same manner as above to form a second layer of silicate salt 20 over the first inner layer 18. Unlike the first exposure to the sodium silicate solution used to create the inner layer 18, the length of exposure to the sodium silicate solution to form the second layer 20 is not as critical. Again, by controlling the drying temperature and the drying time, the amount of sodium silicate converted into silicon dioxide may be selectively controlled.
  • relatively smooth, hard protective layers 14 and 25 may be formed on the surface of the article 10, comprising one or two inner layers of silicate salt 18 and 20, covered by outer bi-layers 22 or 28, respectively.
  • the protective layers 14 and 25 are very resistant to abrasion and corrosion caused by acidic, alkaline, and salt water action, and are glass-like in appearance. These layers can be covered with organic compositions, such as paints, varnishes, and the like.
  • each inner layer of sodium silicate 18, 20 may affect the overall functioning of the protective layers 14 and 25.
  • Such cracks or pores may be in part due to the thermodynamic properties of the underlying materials being treated.
  • One way of overcoming this problem is discussed below with regard to drying a silicate-containing solution at different initial and final temperatures and for differing amounts of time.
  • Another way of dealing with this problem is to expose each lower layer of silicate salt 18 or 20 to an acid before forming a subsequent layer of silicate salt thereover. In this way a plurality of bi-layers may be formed over the fixed surface 12.
  • Figure 3 shows a third protective layer 50 formed on the exposed surface of article 10 comprising two bi-layers 52 and 55 formed over the fixed surface 12 of article 10.
  • the two bi-layers 52 and 55 are manufactured over the fixed surface 12.
  • Film layer 16 is first formed over the fixed surface 12.
  • An inner bi-layer 52 comprising a first layer of silicate salt 18 and first layer of silicon dioxide 54 is then formed over the fixed surface 12.
  • an outer bi-layer 55 is formed thereover comprising a second layer of silicate salt 20 and an outer layer of silicon dioxide 57.
  • an additional bi-layer may be formed over the fixed surface 12.
  • the fixed surface 12, film layer 16 and first layer of silicate salt 18 are first formed on the article 10 using the process cited above.
  • the first layer 18 After the first layer 18 has dried completely and partially been converted into silicon dioxide, it is then immersed in phosphoric acid heated to between about 120°F and 140°F for about 15 to 30 seconds in order to form an inner layer of silicon dioxide 54.
  • the inner layer 54 is similar to the outer layer 24 created when forming the protective layer 14.
  • the inner bi-layer 52 is then exposed to an 18-33% (v/v) sodium silicate solution for about one to three minutes and dried to form a second layer of sodium silicate 20 thereover.
  • the second layer 20 is then immersed in hot phosphoric acid as above for about 15 to 30 seconds to form the outer layer of silicon dioxide 57 thereover.
  • the inner and outer bi-layers 52 and 55, respectively, are formed over the article 10.
  • a protective layer 34 can be formed on the exposed surfaces of an article 30 made of wood.
  • a fixed surface 32 should first be formed on the article 30 so that the protective layer 34 will properly adhere to the article 30.
  • the fixed surface 32 is formed by washing and rinsing it with hot or warm water and a detergent for several minutes to remove all dirt particles or foreign substances from the wood pores. Since wood is more porous than most metallic substances, washing the wood surface and removing foreign substances is more important than with metallic surfaces. Unlike the process used on metallic surfaces, no acid is used to create the fixed surface 32.
  • the fixed surface 32 After the fixed surface 32 has been prepared, it is then exposed to a silicate-containing solution as described above. In a preferred embodiment, the fixed surface 32 is exposed to an 18-33% (v/v) solution of sodium silicate for between about one and three minutes. During this step, the sodium silicate solution is allowed to soak into the wood pores and surface cracks to form a first layer of silicate salt 36. After exposure, the first layer of sodium silicate 36 is then dried at or near room temperature. Higher temperatures may be used, as tolerated by the wood article. It is postulated that during the exposure to the sodium silicate solution, this solution is absorbed into the wood fibers, and that as the silicate material dries it hardens and forms crystal structures between the wood fibers.
  • the first layer of silicate salt 36 is relatively hard and tightly bound to the fixed surface 32.
  • subsequent second and third layers of silicate salt 38 and 40 are formed over the first layer 36.
  • the third layer of silicate salt 40 After the third layer of silicate salt 40 has dried, it is then exposed to an acid, as in the treatment of the article 10.
  • an acid in the treatment of the article 10.
  • 20% to 25% (v/v) phosphoric acid is used at a temperature of 120°F-180°F for about 3 minutes.
  • the outer layer 40 is converted into a bi-layer 41 comprising an outer layer made of silicon dioxide 42 and the inner layer made of inner layer 40.
  • a hard, smooth protective layer 34 is formed over the fixed surface 32 of article 30 comprising two inner layers silicate salt 36, 38, covered by bi-layer 41.
  • an alternative protective layer 45 comprising one inner layer of silicate material 36 and one outer bi-layer 41. The following examples are used to illustrate the methods described above.
  • Samples 1 and 2 were first cleaned with a detergent and water and then immersed in a 25% solution of ortho-phosphoric acid at 140°F for three minutes. The acid solution was heated to speed up the reaction and to provide a more uniform appearance. Samples 1 and 2 were then removed from the acid solution with sample 1 having a dark black smutty film and sample 2 having a light grey smutty film. The smutty films on both samples were desmutted by wiping each sample with a sponge and hot water.
  • samples 1 and 2 have a distinct silvery-white color. It is believed that this color is due to the formation of aluminum ortho-phosphate on the surface of each sample.
  • Samples 1 and 2 were then cooled by placing them in a 60°F water bath for one minute. While wet, the samples were then placed in a 16% sodium silicate solution for one minute. Samples 1 and 2 were then removed from the sodium silicate solution and placed in an oven heated to 300 to 315°F for approximately thirty minutes to dry. After ten minutes, samples 1 and 2 were removed from the oven and allowed to cool to room temperature. It was noted that both samples 1 and 2 have a smooth, glassy surface. Once cooled, samples 1 and 2 were returned to the 18% sodium silicate solution for three minutes . Samples 1 and 2 were then placed back into the heated over for thirty minutes, then removed and allowed to cool to room temperature. When cooled, samples 1 and 2 were again placed in the 25% ortho-phosphoric acid for three minutes.
  • samples 1 and 2 appear hard, smooth, and glassy.
  • the anti-corrosive properties of sample 1 and 2 were tested using ASTM B-117 or Mil. Specifications, C-5541.
  • the paint adhesion property of samples 1 and 2 were also tested to Mil. Specifications, C-5541.
  • Both samples 1 and 2 passed, according to the specifications for each test.
  • the heat and fire resistant property of each sample was tested by comparing the burning of an untreated piece of similar aluminum with the treated samples.
  • the treated and untreated samples were exposed to an acetylene flame which burns between 2,000°F and 2,500°F.
  • the untreated samples decomposed to ash in approximately 30 seconds. No pooling residue was noted.
  • the treated aluminum samples 1 and 2 bent after a few seconds of exposure. After approximately 2 minutes, 8 seconds, the aluminum material began slowly running out from between the two sides of the coating layer. At that point the test was then stopped. No aluminum ash residue was found.
  • Samples 1-3 were first cleaned with a detergent and hot water to remove grease and oil and then immersed in 25% (by volume) solution of ortho-phosphoric acid maintained at 120°F. This step provides iron ortho-phosphate on the surfaces of the panels to which sodium silicate may bond. Samples 1-3 were then rinsed with cool water and immersed in a 33% (by volume) sodium silicate solution maintained at 40°F. The samples 1-3 were then dried at 305°F for 30 minutes to form a first layer of sodium silicate partially converted into silicon dioxide on the exposed surfaces.
  • Samples 1-3 were allowed to cool to room temperature and then immersed in a 25% (v/v) solution of ortho-phosphoric acid at 120°F for approximately 15 seconds. This step forms a hard, insoluble layer of silicon dioxide over the first layer of sodium silicate, thereby creating a bi-layer structure over the surface. Samples 1-3 were then rinsed and cooled and re- immersed in the 33% of sodium silicate solution to form a second layer of sodium silicate over the exposed surfaces. Samples 1-3 were then dried at 305°F for approximately 30 minutes and allowed to cool to room temperature. Samples 1-3 were then immersed in a 25% (v/v) ortho-phosphoric acid solution at 120°F for approximately 15 seconds to form a bi- layer structure of sodium silicate and silicon dioxide over the samples.
  • Samples 1-3 were then rinsed with cool water and dried at 305°F for 5 minutes. Samples 1-3 were tes ' ted in accordance with ASTM-B117 salt spray test and passed successfully the 1/3 hour, 1 hour, 2 hour, and 24 hours tests, which indicates that the protective layer formed in the process acts as a corrosion inhibitor under standard testing conditions.
  • a method for treating copper or copper alloy surface using the foregoing embodiment of the present invention is as follows: A sample of copper tubing was treated. The tubing measured 12 inches (L) x 1/2 inches (I/D) x 1/8 inches side thickness. The sample was first cleaned with a detergent and hot water to remove grease and oil and then immersed in the 25% (v/v) solution of ortho-phosphoric acid at 120°F. This step provides a film layer of copper ortho-phosphate on the exposed surface of the sample to which, it is postulated, sodium silicate can bond. The sample was then rinsed with cool water and immersed in 33% (by volume) sodium silicate solution maintained at 40°F.
  • the sample was then dried at 305°F for approximately 30 minutes to form a first layer of sodium silicate and silicon dioxide over the film layer.
  • the sample was then allowed to cool to room temperature and then immersed in a 25% (v/v) ortho-phosphoric acid solution at 120°F for 15 seconds.
  • the sample was then rinsed with cool water and re-immersed in a 33% (by volume) sodium silicate solution to form a second layer of sodium silicate over the surface.
  • the sample was then dried at 305°F for approximately 30 minutes and allowed to cool to room temperature.
  • the sample was then immersed in the 25% (v/v) ortho-phosphoric acid solution at 120°F for approximately 15 seconds to form an outer layer of silicon dioxide over the second layer of sodium silicate.
  • the sample was then rinsed with cool water and dried at 305°F for 5 minutes.
  • the sample was tested in accordance with ASTM-B117 salt spray test and passed successfully the 48 hour test, indicating that the protective layer formed in the process acts as a corrosion inhibitor under standard testing conditions.
  • EXAMPLE 4 A method of treating a wood surface using the foregoing embodiment of the present invention is described as follows: A wood sample made of pine is first cut measuring 2 inches (W) x 4 inches (L) x 6 inches (H) . A 20% solution of sodium silicate is then pored into a container measuring 18 inches (H) x 6 inches diameter. The container has an air valve (also known as a "Shrader" valve) and a sealing lid so that pressure could be held inside the container when closed. The wood sample is then placed into the container filled with the sodium silicate solution. The container was then closed and sealed tight. An air hose was connected to the air valve and air was forced into the container to create an internal pressure of approximately 70 psi.
  • the wood sample remained in the solution under pressure for ten minutes and then removed and allowed to dry for two hours at 90°F.
  • the wood sample was returned to the sodium silicate solution and placed under pressure as described above.
  • the wood sample was then dried for two hours at 90 degrees Fahrenheit. Once dry, the wood sample was placed into a 25% (v/v) ortho-phosphoric acid solution at 140°F for 5 minutes.
  • the wood sample was then removed from the acid solution and rinsed with cool tap water to wash off the excess acid. The wood was then left to dry for 2 more hours. Once dry, the sample was slightly darker in appearance. No other surface changes were visible.
  • the heat and flame resistance of the wood sample was tested as follows: The treated wood sample and untreated sample were exposed to an acetylene flame which burns at a temperature between 2,000°F - 2,500°F. The treated and untreated samples were exposed to the flame for one minute. Within seconds of being exposed, the untreated sample burned with a visible flame and smoke. Burning continued for approximately ten minutes. With the treated sample, combustion occurred within seconds after being exposed to the flame. After removing the flame, however, combustion stopped within three seconds, and after 15 seconds, no smoke was detected. After 30 seconds, the surface of the treated sample was slightly warm to the touch.
  • Samples 1-3 were first cleaned with a detergent and hot water to remove grease and oil and then immersed in a 25% (v/v) solution of ortho- phosphoric acid at 120°F. This step provides magnesium ortho- phosphate to which it is postulated the sodium silicate may bond. The samples were then rinsed with cool water and immersed in a 33% (v/v) 40°F sodium silicate solution for 5 minutes. The samples were then dried at 305°F for 10 minutes to form a first layer of sodium silicate.
  • the panels were allowed to cool to room temperature and then immersed in a 25% (v/v) solution of ortho-phosphoric acid at 120°F for 15 seconds (this step can vary from 15 to 45 seconds) .
  • a uniform, outer layer of silicon dioxide was thereby formed on the surface exposed to the acid solution.
  • the samples were then rinsed with cool water and re-immersed in the 33% (v/v) sodium silicate solution.
  • the samples were then dried at 305°F for 30 minutes and allowed to cool to room temperature.
  • the samples were then immersed in a 25% (v/v) ortho-phosphoric acid solution at 120°F for 15 seconds, forming a final layer of silicon dioxide.
  • the samples were then rinsed with cool water and dried at 305°F for 5 minutes.
  • a sample of nickel plated tubing was treated - the sample was nickel plated measuring 12 inches (1) c 1/2 inch (O.D.) and 1/8 inch side wall thickness.
  • the sample was first cleaned with a detergent and hot water to remove grease and oil and then immersed in a 25% (v/v) solution of ortho- phosphoric acid at 120 degrees Fahrenheit. This step provides nickel ortho-phosphate to which the sodium silicate may bond.
  • the sample was then rinsed with cool water and immersed in a 33% (v/v) 40 degree Fahrenheit sodium silicate solution for 5 minutes.
  • the sample was then dried at 305 degrees Fahrenheit for 10 minutes to form a first layer of sodium silicate. During the drying process, a portion of the sodium silicate was partially converted into silicon dioxide.
  • the sample was allowed to cool to room temperature and immersed in a 25% (v/v) solution of ortho-phosphoric acid at 120 degrees Fahrenheit for 15 seconds (this step can vary from 15 to 45 seconds) . A uniform outer layer of silicon dioxide is thereby formed on the surface exposed to the acid solution.
  • the sample was then rinsed with cool water and re-immersed in the 33% sodium silicate solution.
  • the sample was then dried at 305 degrees Fahrenheit for 10 minutes and allowed to cool to room temperature.
  • the sample was then immersed in a 25% ortho-phosphoric acid solution at 70 degrees Fahrenheit for 5 minutes forming a final layer of silicon dioxide.
  • the sample was then rinsed with cool water and dried at 305% for 5 minutes to dry.
  • EXAMPLE 7 A method for treating a silver or silver alloy surface using the foregoing embodiment of the present invention is described as follows: A sample of silver plated tubing was treated. The sample measured 12 inches (L) 1/2 inch (O.D.) and had 1/8 inch side wall thickness. The sample was first cleaned with a detergent and hot water to remove grease and oil and then immersed in a 25% (v/v) solution of ortho-phosphoric acid at 120°F. This step provides silver nitrate on the surface of the silver, to which it is postulated the sodium silicate bonds. The sample was then rinsed with cool water and immersed in a 33% (v/v) 40°F sodium silicate solution for 5 minutes.
  • the sample was then dried at 305°F for 10 minutes to form a first layer of sodium silicate. During the drying process, a portion of the sodium silicate was partially converted into silicon dioxide. The sample was allowed to cool to room temperature and then immersed in a 25% (v/v) solution of ortho-phosphoric acid at 70°F for 5 minutes. A uniform outer layer of silicon dioxide is thereby formed on the surface exposed to the acid solution. The sample was then rinsed with cool water and re-immersed in the 33% (v/v) sodium silicate solution. The sample was then dried at 305°F for 10 minutes and allowed to cool to room temperature. The sample was then immersed in a 25% (v/v) ortho-phosphoric acid solution at 70°F for 5 minutes, forming a final layer of silicon dioxide. The sample was then rinsed with cool water and dried at 305°F for 5 minutes.
  • EXAMPLE 8 A method for treating titanium or titanium alloy surface using the foregoing embodiment of the present invention is described as follows:
  • a sample of titanium plate was treated - the sample measured 3 inches (L) x 3 inches (W) and 0.02 inches thick.
  • the sample was first cleaned with a detergent and hot water to remove grease and oil and then immersed in a 10% (v/v) solution of ortho-phosphoric acid at 120°F. This step provides titanium ortho-phosphate and titanium oxide on the surface of the titanium with which it is postulated the sodium silicate may bond.
  • the sample was then rinsed with cool water and immersed in a 33% (v/v) 40°F sodium silicate solution for 5 minutes.
  • the sample was then dried at 305°F for 10 minutes to form a first layer of sodium silicate. During the drying process, a portion of the sodium silicate was partially converted into silicon dioxide.
  • the sample was allowed to cool to room temperature and immersed in a 25% (v/v) solution of ortho-phosphoric acid at 70°F for 5 minutes. A uniform outer layer of silicon dioxide is thereby formed on the surface exposed to the acid solution.
  • the sample was then rinsed with cool water and re-immersed in the 33% (by volume) sodium silicate solution. The sample was then dried at 305°F for 10 minutes and allowed to cool to room temperature. Then, the sample was immersed in a 25% (v/v) ortho-phosphoric acid solution at 70°F for 5 minutes, forming a final layer of silicon dioxide. The sample was then rinsed with cool water and dried at 305°F for 5 minutes.
  • the present method can be used to treat any relatively rigid surface in order to protect the surface of that material.
  • Metals such as aluminum, steel, zinc, and magnesium, have been found to be particularly suited for treament according to this embodiment.
  • Those of skill in the art will be able to determine, through routine experimentation, those materials or surfaces which cannot be treated according to this embodiment of the invention to produce a protective layer on the surfaces of such materials.
  • materials which will degrade due to the drying temperatures employed in this embodiment of the present method or due to adverse chemical reactions with any of the chemicals or reagents, such as the silicate solution, used in this embodiment will probably not be practical to use as surfaces on which to form the protective layer according to this embodiment of the present invention.
  • experimentation can, for example, consist of subjecting a surface made from a particular material to the present method to determine whether a protective layer can be formed thereon.
  • the protective layer formed according to this embodiment of the present invention is most effective when the silicate- containing solution used to form the protective layer can be applied as a uniform layer 63 to a rigid surface 61 on which it is desired to form the protective layer.
  • hydrophilic as used herein describes a surface on which water and/or other liquids will form a uniform, continuous wet film or layer.
  • a hydrophilic surface is one which will act to carry a liquid, such as water or an aqueous solution, so that when the liquid is applied to such a surface the liquid spreads evenly over the entire surface in a uniform, continuous wet film or layer.
  • a liquid such as water or an aqueous solution
  • Surfaces can be rendered hydrophilic by any means known to the art. The removal of excess oxides, oils, and other contaminants on a surface, such as the surface of a metal, is often sufficient to render that surface hydrophilic. Methods such as sanding, sandblasting, and using various chemical cleaners can be used to remove such oxides, oils, and other contaminants.
  • the rigid surface 61 is a metal surface
  • the hydrophilic surface 62 can be formed by exposing that surface to an acid, preferably an acidic solution such as a solution of 20% to 25% (by volume) phosphoric acid. The phosphoric acid acts as a "chemical sandpaper" to render the surface hydrophilic.
  • a uniform, continuous film or layer 63 of a silicate-containing solution can be applied to the rigid surface 61 to be treated. It is believed, however, that methods of providing a uniform layer of the silicate-containing solution on the surface being treated other than applying the silicate solution to a hydrophilic surface can also be used to perform the present method. For example, a gel or emulsion containing a silicate material could instead be applied to a surface such that a continuous, relatively uniform layer of the gel is spread over the surface. Alternatively, the silicate solution can be sprayed on the rigid surface. The surface would then be treated as in the remaining steps of the present method.
  • the surface 62 is preferably rinsed in order to remove impurities and/or chemical cleaning residues from the surface. Such rinsing can be accomplished by applying water, preferably at a temperature of between approximately 68°F and 140°F, to the hydrophilic surface 62. The surface 62 can then be dried.
  • a silicate-containing solution is next applied to the cleaned, hydrophilic surface 62 so as to form a continuous, thin layer 63 of the solution on the hydrophilic surface 62.
  • the silicate-containing solution is a sodium silicate solution, comprising silicon dioxide, silicic acid (H 2 Si 2 0 5 ) , sodium oxide, and water (available from the PQ Corporation, Tacoma, WA as Liquid N or Liquid 0) .
  • silicate-containing solutions made up of other silicate compounds can also be used.
  • Solutions of potassium silicate, metallo-silicates (including aluminum silicate, magnesium silicate, iron silicate, copper silicate, zinc silicate, and manganese silicate) , and organo-silicates can be used, where potassium, other metals, or organic compounds replace the sodium in a sodium silicate solution.
  • KASIL #1 a potassium silicate solution available from the PQ Corporation, can be used in place of a sodium silicate solution.
  • the silicate-containing solution is made up of between approximately 10% and 100% by volume of a silicate compound, such as sodium silicate or potassium silicate.
  • the solution contains between 20% and 40% (by volume) of the silicate compound.
  • the solution is also preferably applied when at a temperature of between approximately 68°F and 140°F.
  • the hydrophilic surface 62 is exposed to the silicate- containing solution for between approximately 1 and 60 seconds, and preferably between 1 and 20 seconds. In one embodiment, such exposure is accomplished by immersing the surface of the material being treated. Such exposure of the hydrophilic surface 62 to the silicate-containing material, however, should be minimized in order to provide the treated surface with enhanced corrosion resistance.
  • the solution is dried. In a preferred embodiment, such drying can be accomplished by exposing the surface of the treated material to an environment having an initial temperature of between 68°F and 480°F, and preferably having an initial temperature of between 120°F and 150°F.
  • the temperature of the environment surrounding the treated hydrophilic surface is then raised by between approximately 30°F per minute and 60°F per minute until a final temperature of between about 302°F and 480°F, and preferably between 305°F and 350°F, is reached.
  • a final temperature between about 302°F and 480°F, and preferably between 305°F and 350°F.
  • the temperature of the silicate-containing solution and the surface underlying it is raised from a lower initial temperature to a higher temperature.
  • the environement surrounding the surface can be at a higher initial temperature, since the surface will itself rise in temperature slowly due to its low thermal conductivity. It is important, however, that the silicate-containing solution/dried silicate material reach a temperature of at least 302°F during this drying step.
  • the drying of the layer of silicate-containing solution 63 can be accomplished, for example, by placing the treated surface in a drying oven.
  • Other methods known to those of skill in the art are, of course, also possible.
  • infrared radiation from a heat lamp can also be used to dry the layer of the silicate-containing solution 63 and raise it to a temperature above 302°F.
  • agents can be added to the silicate-containing solution to aid in the drying and hardening of the layer 63.
  • Zinc oxides when present in such a solution in an amount of up to 7% (by volume) of the solution, will assist in the hardening of the solution.
  • the drying time for a film or layer 63 of the silicate- containing solution on the hydrophilic surface 61 will depend in part on the thickness of the film or layer 63 , the form or shape of the surface and article being treated, and the composition of the material being treated.
  • a material with a high thermal conductivity such as aluminum
  • the present method will work best on a material with a lower thermal conductivity when that material is first exposed to a higher temperature.
  • an appropriate drying time will be between approximately 2 and 50 minutes, and preferably between 6 and 15 minutes.
  • an acidic solution used in this embodiment can comprise between 1% and 99% (by volume) of an acid, and preferably between 10% and 30% (by volume) of such an acid.
  • the acidic solution used is a phosphoric acid solution, because phosphoric acid is cheap, relatively safe, and widely available.
  • other acids can also be used.
  • gaseous carbon dioxide which is a weak acid, can be passed over or through the surface being treated.
  • a gaseous acid such as carbon dioxide is particularly useful when the surface being treated is relatively porous, such as a wood surface.
  • the acidic solution is preferably at a temperature of between approximately 68°F and 180°F when applied to the dried layer of silicate material 65.
  • Any method of applying the acidic solution to the dried silicate layer 65 known to those of skill in the art can be used.
  • the surface to which the silicate- containing solution was applied encompasses the entire surface of an article or even just the entire surface of one member of an article, the article or member can be immersed or "dipped" in the acidic solution.
  • the acidic solution can be applied to a surface that comprises only part of an article or a member of an article by spraying the acidic solution onto the article, or by any other means.
  • the acidic solution is preferably exposed to the layer of silicate material for between about 5 seconds and 120 seconds. More preferably, the acidic solution is exposed to the layer for between 20 seconds and 50 seconds.
  • the protective layer is formed on the surface being treated.
  • the protective layer comprises an outer layer 67 exposed to the acid, made up of mostly silicon dioxide, and an inner layer made up of the dried silicate material 65.
  • the dried silicate material 65 comprises both silicon dioxide and other oxides.
  • the silicate-containing solution is sodium silicate
  • the dried silicate material will be made up of silicon dioxide and sodium oxide.
  • the surface being treated is can be rinsed to remove excess acidic solution.
  • rinsing can be accomplished by applying water, preferably at a temperature of between approximately 68°F and 140°F, to the treated surface. Water can be applied to the surface either by spraying or by immersion in water or by any other means. The surface is then allowed to dry.
  • each protective layer should be rinsed after the formation of the protective layer in order to remove excess acid before next applying a new layer of the silicate- containing solution.
  • a plurality of protective layers can be formed on a surface.
  • the protective properties of the protective layer can be enhanced. For example, the corrosion resistance of a piece of metal on which the protective layer of the present invention has been formed can be increased by increasing the number of protective layers on that piece of metal.
  • sample 1 comprises 2024 T-3 stock while sample 2 comprises 6061 T-6 stock. Both panels measure 3 inches (W) x 10 inches (L) and .039 inches thick.
  • the surfaces of Samples 1 and 2 are provided with hydrophilic surfaces by wet sanding the surfaces of the panels with an electric hand sander for 5 minutes. These hydrophilic surfaces are then rinsed with a detergent and water. While wet, the samples are immersed in a 16% (by volume) sodium silicate solution for 20 seconds at approximately room temperature in order to coat the panels with a uniform layer of the sodium silicate solution. Samples 1 and 2 are then removed from the sodium silicate solution and placed in an oven heated initially to about 130°F.
  • samples 1 and 2 are removed from the oven and allowed to cool to about 100°F. Once cooled, samples 1 and 2 are immersed in a 25% (by volume) ortho-phosphoric acid solution for 40 seconds. Following this, the surfaces of samples 1 and 2 are rinsed to remove excess ortho-phosphoric acid solution.
  • samples 1 and 2 appear hard, smooth, and glassy.
  • the anti-corrosive properties of sample 1 and 2 are tested using ASTM B-117 and Mil. Specifications, C-5541. These samples are subjected to such tests for 168 and 336 hours, and are found to exceed the standards specified by these tests.
  • the paint adhesion properties of samples 1 and 2 are also tested to Mil. Specifications, C-5541. Both samples 1 and 2 pass, according to the specifications for each test.
  • each sample The heat and fire resistant properties of each sample are tested by comparing the burning of an untreated piece of similar aluminum with the treated samples.
  • the treated and untreated samples are exposed to an acetylene flame which burns between 2,000 and 2,500 degrees Fahrenheit.
  • the untreated samples decompose to ash in approximately 30 seconds.
  • the treated aluminum samples 1 and 2 bend after a few seconds of exposure. After approximately 2 minutes, the aluminum material begins slowly running out from between the two sides of the coating layer.
  • EXAMPLE 10 A Method for Treating a Steel Surface Three samples of steel panels 1-3 made of 4130 steel are treated, all measuring 4 inches (W) and 6 inches (L) and 0.041 inches thick. The surfaces of Samples 1-3 are provided with hydrophilic surfaces by wet sanding the surfaces of the panels with an electric hand sander for 5 minutes each. These hydrophilic surfaces are then rinsed with a detergent and water. While wet, the samples are immersed in a 16% (by volume) sodium silicate solution for 20 seconds at approximately room temperature in order to coat the panels with a uniform layer of the sodium silicate solution. Samples 1-3 were then placed in an oven at 310°F for 12 minutes. After 12 minutes, samples 1-3 are removed from the oven and allowed to cool to about 100°F. Once cooled, samples 1-3 are immersed in a 25% (by volume) phosphoric acid solution for 40 seconds. Following this, the surfaces of samples 1-3 are rinsed to remove excess phosphoric acid solution.
  • Samples 1-3 were tested in accordance with ASTM-B117 salt spray test and passed successfully the 1/3 hour, 1 hour, 2, 24, 48, and 96 hours tests, which indicates that the protective layer formed in the process acts as a corrosion inhibitor under standard testing conditions.

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Abstract

L'invention concerne un procédé permettant de former une couche protectrice (14) sur une surface rigide (12), comme une surface rigide en métal ou en bois, afin de la protéger de l'abrasion, de la corrosion, de la chaleur et du feu. On procède tout d'abord à la préparation de la surface de l'article. La surface d'articles en métal peut être nettoyée puis exposée à de l'acide phosphorique concentré. La surface d'articles en bois peut être nettoyée méticuleusement uniquement avec de l'eau chaude et un détergent. La préparation de la surface s'opère de préférence de manière à ce qu'une pellicule continue et uniforme de liquide puisse se former sur ladite surface. Après que la surface ait été préparée, on lui applique une solution contenant 10 à 16 % (v/v) de silicate pendant 20 secondes et on laisse sécher complètement à 305 °F afin de former une couche de matière silicate (18) sur toute la surface. Pendant le séchage, au moins une partie du silicate de sodium est transformée en dioxyde de silicium. On applique ensuite un acide sur la surface afin de former une couche qui la protège.
PCT/US1993/011279 1992-11-20 1993-11-19 Procede permettant de proteger une surface a l'aide de composes silicates WO1994012289A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP94902326A EP0701489A1 (fr) 1992-11-20 1993-11-19 Procede permettant de proteger une surface a l'aide de composes silicates
RU95113589A RU2123894C1 (ru) 1992-11-20 1993-11-19 Способ защиты поверхности с использованием силикатных соединений
JP6513284A JPH08503656A (ja) 1992-11-20 1993-11-19 ケイ酸塩化合物による表面保護方法
BR9307502A BR9307502A (pt) 1992-11-20 1993-11-19 Processo para proteger uma superfície usando compostos de silicato
AU56733/94A AU691794B2 (en) 1992-11-20 1993-11-19 Process for protecting a surface using silicate compounds
KR1019950702049A KR950704057A (ko) 1992-11-20 1993-11-19 규산염 화합물을 사용한 표면 보호 방법(Process for Protecting a Surface using Silicate Compounds)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US97915592A 1992-11-20 1992-11-20
US07/979,155 1992-11-20

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WO1994012289A1 true WO1994012289A1 (fr) 1994-06-09

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KR (1) KR950704057A (fr)
AU (1) AU691794B2 (fr)
BR (1) BR9307502A (fr)
CA (1) CA2149919A1 (fr)
RU (1) RU2123894C1 (fr)
WO (1) WO1994012289A1 (fr)

Cited By (3)

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WO1996022843A1 (fr) * 1995-01-23 1996-08-01 Tigerwerk Lack- U. Farbenfabrik Gmbh & Co. Kg Procede de poudrage ou de vernissage au vernis a cuire de pieces en matieres sensibles a la temperature
WO2013017135A1 (fr) 2011-08-02 2013-02-07 Bollerup Jensen A/S Matière cellulosique comprenant un silicate de métal
WO2013017134A1 (fr) 2011-08-02 2013-02-07 Bollerup Jensen A/S Composition de silicate métallique de faible viscosité

Families Citing this family (1)

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CN109092646A (zh) * 2018-09-27 2018-12-28 浙江宇豪木业有限公司 一种木板喷漆工艺

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US3423229A (en) * 1965-05-17 1969-01-21 Teleflex Inc Coating with zinc and aluminum powder in potassium silicate
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US4120702A (en) * 1976-10-29 1978-10-17 Asea Aktiebolag Treating a silicon steel material having a silicate protective coating thereon with an aqueous solution containing phosphates to form a further protective coating
US4810741A (en) * 1985-12-03 1989-03-07 Kim Jae W Fire-resistant material, noncombustible material for treating interior building material and processes for their production
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996022843A1 (fr) * 1995-01-23 1996-08-01 Tigerwerk Lack- U. Farbenfabrik Gmbh & Co. Kg Procede de poudrage ou de vernissage au vernis a cuire de pieces en matieres sensibles a la temperature
WO2013017135A1 (fr) 2011-08-02 2013-02-07 Bollerup Jensen A/S Matière cellulosique comprenant un silicate de métal
WO2013017134A1 (fr) 2011-08-02 2013-02-07 Bollerup Jensen A/S Composition de silicate métallique de faible viscosité

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RU2123894C1 (ru) 1998-12-27
BR9307502A (pt) 1999-03-16
EP0701489A1 (fr) 1996-03-20
CA2149919A1 (fr) 1994-06-09
JPH08503656A (ja) 1996-04-23
KR950704057A (ko) 1995-11-17
EP0701489A4 (fr) 1995-10-12
AU691794B2 (en) 1998-05-28
AU5673394A (en) 1994-06-22

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