New! View global litigation for patent families

WO1996009423A1 - Organically-based agent for removing rust from surfaces, production and use of said agent - Google Patents

Organically-based agent for removing rust from surfaces, production and use of said agent

Info

Publication number
WO1996009423A1
WO1996009423A1 PCT/EP1995/003670 EP9503670W WO9609423A1 WO 1996009423 A1 WO1996009423 A1 WO 1996009423A1 EP 9503670 W EP9503670 W EP 9503670W WO 9609423 A1 WO9609423 A1 WO 9609423A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
iron
fe
rust
corrosion
according
Prior art date
Application number
PCT/EP1995/003670
Other languages
German (de)
French (fr)
Inventor
Peter M. Kunz
Hans ZÄHNER
Monika Willrett
Stefan Dausmann
Michael Paul
Original Assignee
Kunz Peter M
Zaehner Hans
Monika Willrett
Stefan Dausmann
Michael Paul
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

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DEGREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DEGREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/24Cleaning or pickling metallic material with solutions or molten salts with neutral solutions

Abstract

The invention concerns an agent, based on organic compounds obtained from micro-organisms, for removing rust from metal surfaces corroded with iron oxides. Rust is normally removed from metal articles using corrosive baths containing organic and/or inorganic acids which, owing to the concentrations used, must meet certain safety requirements and entail costly disposal procedures once the baths are depleted. Iron-absorbing products obtainable using biological methods are generally active in the neutral pH range, eliminating the salt production and contamination of the effluent associated with the neutralisation process normally required. Rust can be removed using reproducible intra- or extra-cellular products which have a high affinity with iron ions. The proposed agents are produced by culturing appropriate organisms in a suitable medium in such a way that they are stimulated to produce these agents. The articles requiring de-rusting are then treated by being dipped in or painted with the agent. Provision of appropriate supports to immobilise the articles facilitates use of the agents and permits recycling of the agent by suitable treatment.

Description

Means for rust removal of surface organic-based as well as its preparation and use

description

The invention provides means for rust removal of Oberflä¬ chen (elimination of corrosion products). Furthermore, the invention relates to a method of forming and a process for use of these An¬ derusting agent.

By definition according to DIN 50900, the first 1 refers to the "reaction of a metallic material with its environment, which causes a measurable change in the material and can lead to ei¬ ner impairment of the function of a metal component or an entire system from corrosion. In most cases, this reaction is electrochemical in nature, However, in some cases it may be chemical (non-electrochemical) or metallophysikali- shear nature. " [Meckelburg, E .: corrosion behavior of materials, VDI Verlag]

The world economy from corrosion damage and consequential costs arising losses are schungs- international Materi- and economic institutes estimated at many billions of dollars per year. This shows that corrosion of particular trächtlichem economic interest. [Meckelburg, E .: Kor¬ rosionsverhalten of materials, VDI Verlag, Düseidorf 1990]

The corrosion of a material is a very complex and viel¬ layered process, whose exact sequence respectively depends on the specimen at the system of the material and its environment. Corrosion must therefore always be considered individually. Nevertheless, we can make some basic statements that are applicable for all corrosion reactions. Korrosionsreak¬ functions are always interfacial reactions between corrosive material and its vicinity. The corroding metal is attacked by oxidation in a redox reaction.

Me → Me z + + ze 'A metal is be¬ characterized as passive with respect to its corrosion behavior when in the circumstances Korrosionsge¬ high speeds are expected, but the corrosion-forming (usually oxide) top layers proceeds very slowly due to. These top layers are usually the corrosion itself.

As an example, the high corrosion resistance = the with a normal potential of Eo - 1, called V 66 very base of aluminum, resulting from the formation of a stable, non-conducting oxi¬ sized top layer. [Kaesche, H .: The corrosion of metals, 3rd ed., Springer Verlag 1990].

In the case of iron, a passivating oxide layer can also be formed. Here are the corrosion conditions aus¬ decisive. The iron (II) hydroxide is much more water soluble, as Fe (OH) 3, which a partial hydroxide of the formula FeO (OH) or Fe2θ3- * H2O. Immersed pure iron unmoved in destillier¬ tes water, the Fe formed + + and OH "ions diffuse away from the metal surface, and 3 (= rust) are first oxidized in a range of higher oxygen concentration to Fe (OH). The at some distance from the metal surface precipitated oxides do not form a protective layer on the metal and the corrosion proceeds. in contrast, the oxygen concentration at the metal surface is large in a moving sample in the same water and results in the formation of an invisible Oxidfil- mes on the surface, whereby the samples will not corrode, but remain glossy [Kaesche, H .: the corrosion of metals, 3rd edition, Springer Verlag 1990, Evans, UR. introduction to the corrosion of metals, Verlag Chemie, 1965].

Iron is one of the base metals (Eo = -0.44 V) and is therefore particularly susceptible to electrochemical destruction. The Hauptkor¬ rosionsprodukt of iron rust. The rusting of iron is a naturally flowing process. As pure metal iron is thermodynamically unstable and therefore attempted in the thermodynamically stable sized state, the grate to pass [Ute Rasemann: Untersu¬ deviations of rust layers to clarify their macroscopic and microscopic structure and some properties that Teilvor- transitions of the complex characterize Rostungsmechanismus. Frei¬ mountain, 1975].

Rust is described chemically as often hydrated iron (III) oxide (FeO (OH) = V2 Fe2θ3- * H2O). Specifically, it is ever nevertheless, the rust as a mixture of different proportions of iron (II) oxide (FeO), iron (II, III) oxide (Fe3θ4), and as the most frequent component of iron (III) oxide (Fe2θ3 ) to characterize. Water can be present as the hydrate or hydroxide.

By definition, [Encyclopedia of Corrosion Volume 1: Mannesmannrόhren- plants, 1970] is meant by rust "the first light ent fernbaren rust arising in the atmosphere on steel". Charak¬ teristic for the rust his initial appearance on metal is talloberflächen as small pixels, then increasingly growing together.

Rust is "inscribed deposits of corrosion products be¬, which did not occur at that point, but have been taken place from somewhere else .... Through these deposits may be creating ge conditions for ventilation elements and rust spots occur" as.

The most common corrosion product of iron Fe2θ3 produced the following overall equation:

4 Fe + 3 O2 → 2 Fe2θ3 or for FeOOH

4 Fe (Me) 3 0 + 2 (D + 2 H 2 0 (l) → 4 FeOOH (s)

Me = metal, I = liquid, S = solid

The equation shows that not the free oxygen in the air, but is dissolved in the electrolyte, responsible for the oxidation. Thus, the diffusion of soluble oxygen to the metal of the rate-keitsbestimmmende step of corrosion.

This equation can be further broken down, causing the layer-like structure of the grid can be explained. First, the formation of the unstable iron takes place (II) oxide, which can be darsteilen doxgleichung by the following re:

Fe → Fe 2+ + 2e "(Ox.) Vz O2 + 2e" → θ2- (Red.)

The very unstable FeO reacts in the presence of water and oxygen continue to Fe (OH) 2 / which erstoff by the dissolved Luftsau¬ is oxidized to Fe (OH). 3

'Λ O2 + 2e "→ O 2' θ2- + H2O → 2 OH '

Fe 2 + + 20H → Fe (OH) 2 2 Fe (OH) 2 + 2 'θ2 + H2O → 2 Fe (OH) 3 and

Fe (OH) 3 → FeOOH + H2O = y 2 Fe2θ3 '* H2O + H2O

The middle mixed oxide layer of Fe3θ4 comes from the fact that by the formation of iron (III) oxide coating partially Sau¬ erstoffzufuhr of the lower layers is blocked. Thus Fe + can not + be oxidized completely to Fe *. The formation die¬ ser protective layer explains the increasingly slower rates of Rostbil¬-making over time. Therefore, a rust layer can be principles-Piell represented as follows:

■ hematite [iron (III) oxide]

■ magnetite [Eisem (II, III) oxide]

■ wustite [iron (II) oxide]

■ iron

In practice, one will hardly find this layer structure clearly defined. The top iron (III) oxide layer is brittle on drying and bursting places from. Thus, the oxide layers and lower down of metallic iron are exposed, making them come into contact with O2 and can be oxidized. Microscopic observation of a rusted sample reveals a very rugged and lightweight construction. is thus formed over time a very inconsistent in terms of thickness and composition layer of rust, which makes an accurate characterization.

The current available methods of rust removal of surfaces are primarily based on the use of acids as a mordant.

These are, as they are relatively highly concentrated, treated with entsprechen¬ the precautions. Not to neglect the acid concentrations are within the breathing air in Be¬ reaching the pickling tank. Despite some recycling the Beizbä- these are depleted over time and require elaborate disposal. For this purpose, large amounts correspondingly strong alkalis are necessary. For the resulting salt, there is generally no applicational possibility. It has to be dumped costly.

Mechanical methods for removing rust are also possible wer¬, the but used for technical and time constraints, possibly with small rust spots and flat surfaces. In addition, the metal surface is injured here easily, which leads attack surfaces new Korrosions¬.

The object of the invention now was to find an environmentally nenderes, efficient means which is capable of the Ei¬ senoxide of the corroded surfaces in about similar periods Entrostungsbäder conventional peel and concentrate to a high degree, so that for example a direct recovery from the complex is possible.

The object is inventively achieved in that ferritin, as it occurs in the human body iron stores are used. In addition, however are also a variety of complexing agents, siderophores, chromatophores, and other proteins Pro¬ into consideration, all of which have a Affinitä for iron. Quantitatively rusted sheets to demonstrate the effect of rust removal about weight measurements could, rusted with said means and thereby brought back the shine. The agents are found to be produced by fermentation; it can be handled without danger with them, and they can be better disposed of or worked up.

The use of these agents is inventively in immobiliserter

Form on suitable supports, to increase the efficiency and chen to ermögli¬ a simple recovery from the application.

The entrostenden to metal parts are then immersed in a staggered with these agents bath or coated with a correspondingly concentrated solution and after a certain time Einwirk¬ removed.

The following are the agents found are briefly described below:

Ferritin is an iron-protein compound and serves, in addition Hämosi- derin, as an important storage and transport form of iron in the organism Or¬ of vertebrates. Is formed ferritin plasma present at freely in cytokine Polyribosomes. The Eisenanteii is about 20% in the compound. The protein content of ferritin having a molecular weight of 480,000 is called apoferritin [Pschyrembel].

Ferritin is a hollow sphere with a diameter of 1 nm 2, which consists of 24 subunits each about 1 8500-1 9,000 Dalton [man, S .; J .V. Bannister, R.]. P. Williams: Structure and composi- tion of ferritin cores isolated from human spit, limpet (Patella vulgata) hemolymph and bacterial (Pseudomonas aeruginosa) cells (published erratum Appears in] .Mol.Biol, 1986] l of 5, 1 90 (1) : 1 39) J 1 .Mol.Blol 88, 225-232]. A molecule has a storage capacity of up to 4500 iron atoms, which are connected to verschie¬ which amino acids of the protein coat [Mass Over, WH; J .M. Cowley: The ultrastructure of ferritin Macromolecules. The lattice structure of the core crystal lites. Proc. Natl. Acad. Be. Med ZΩ, 3847 - 385 1, (1 973)]. Most ferritins included 1, 000 - 3,000 iron atoms. The protein shell encloses a dense matrix of hydrated iron hydroxide, Fe (OH) 3 combined with a diameter of 7 nm. In addition, phosphorus is in different ratios with this matrix. Other sources spre¬ surfaces of the storage form Eisenoxyhydroxidphosphat (FeOOH) β * (FeO * Pθ3H2) [Harrison, P .; F. Fischbach, T. Hoy, G. Haggis: Nature 2_l_ώ, 1 1 88 - 1 1 90, (1967)]. Ferritin has ligands for Ferrioxidase activity, capable of oxidizing Fe + to Fe ^ + and thus initiate a Eiseninkorporation in ferritin. The iron is out achieved by reduction of Fe ^ + to Fe 2 + using Cheiatbildnern.

When hemosiderin is a water-insoluble iron Ei¬ white connection with about 37% iron content. It is next to ferritin, a storage form of iron in the body.

Transferrin is a glycoprotein (MW 90,000) which is electrophoretic cally located in the fraction of beta-globulins. Normaler¬ example is one-third with iron Untitled gesät¬ (as Fe * +) transferrin, the radical is referred to as free iron-binding capacity. The total binding capacity of transferrin for iron is 45-73 / mol / l (250 to 41 0 g / dl).

To date, besides more than 200 different siderophores ge found were. The structural diversity here is quite large. It is shared (eg Rhizob- actin) and mixed forms hydroxamate (eg desferrioxamine E), catechol (eg enterochelin) or phenol, oxazoline, polycarboxylate. Siderophores are counted metabolites to primary because they are synthesized in the logarithmic growth phase (Trophophase).

In Siederochromen is ferrous or eisenbin- ended natural products that contain Hydroxamsäuregruppierungen in a Mole¬ kül in an arrangement that allows the formation of a Eisenhydrox- amatkomplexes. Thereby selectively Fe ^ + ions are gebun¬ to. The Siderochrome with antibiotic properties are called Sidermycine, those who can act as growth factors as sideramines. For example, a distinction is made acidic ferrioxamines: eg desferrioxamine H ■ * basic ferrioxamines: eg desferrioxamine B => amphoteric ferrioxamines: eg desferrioxamine G.

A ferrioxamine has been used for years in treating Thalassämiekranken that have too much iron in the blood, as well as dialysis patients receiving treatment through an excessive amount of aluminum.

The Ferrichrome was first made in 1952 Ustllago sphaerogena iso¬ lines. There are many Ferrichrome types that are structurally related. These include ferricrocin, Ferrichrysin, Ferri Rubin and Ferrirhodin.

In Side Raminen is cyclic esters of 3 molecules of 2, 3-Dihydroxybenzoylserin. This includes enterochelin, also called Enterobactin which is formed of, eg, E. coli or salmonella typhimurium la.

For the preparation of the agent can be used in addition to the above, the following microorganisms:

- Yersinia H 1 852. - Staphylococcus hyicus DSM 20459, yield to 4, 1 g / l

- E. coli TO 3 1 1

- E. coli 5050 Tu

- Staphylococcus aureus NCTC 1 4990

- Staphylococcus aureus NT 259 - Staphylococcus aureus 31588

- Staphylococcus aureus G4

- Staphylococcus aureus BR 26

- Staphylococcus aureus Sau 3A

- Streptomyces olivaceus Tu 271 8

For the culturing of bacteria for producing the agent is a modified nutrient solution Zähner [Zähner, H.; W. Keller Schierlein, R. Hütter, K. Hess-Leisinger, A. Deer: Stoffwechsel¬ products of microorganisms, 40. Mitt sideramines gillaceen from Asper-.. Microbiol. Arch. 45, 1 19, (1963)] was used:

0, 5 g of CaCl2 * 2 H2O 1, 0 g K2HPO4

2 mg ZnSθ4 * 7 H2O

To disk: 1, 5% agar possibly 100 γ / l Thlamin

20.0 g glucose

20 mg / 1 FeCl3 * 6 H2O

1 00 mg Yeast Extract

1 0 γ biotin least 1000 ml. water

A suitable broth for E. coli TO 3 1 1 to Siederophoren- is education

K2HP04 10.6 g

NaH2P0 4 * 2 H2O 6, 1 g

MgSO 4 * 7 H2O 0.2 g

(NH 4) 2.0 g 2Sθ4

Ca (N0 3) 2 0.01 g

deion FeSθ4 * 7 H2O 0. 5 mg. Water to 1 1

The mushroom broth for Side Ramin formation may look like the following dimensions:

Broth 4 normal medium

Glucose 20 g 20 g

Asparagine H2θ 5 g 5 g

NH 4 Cl - 5 g

K2HPO4 1 g 1 g

MgSO 4 * 7 H2O 1 g 1 g

CaCl2 * 2 H2O 500 mg 500 mg

ZnSθ4 * 7 H2O 2 mg 2 mg

H2O 1 1 1 1 may (with 20 mg / 1 Fe = 13 '* 6 H2O.

Siderophores are characterized,

■ that they are strongly produced from iron deficiency. ■ to hold Fe (IIl) or Fe (II), under physiological conditions in solution,

■ that they Fe (III) or Fe (II), in the growth ausreichen¬ the extent to which or transport into the cell [Neilands, JB; C. Radledge: Mlcrobial iron transport compounds. In: CRC Hand¬ book of microbiology, Vol IV Eds.. Laskin, AI; HA Lechavalier, CRC Press, Boca Raton, Florida, 565-58 1, (1982)] ..

To obtain the siderophores must be used usually in an iron-free environment.

The Siderochrome are excreted gene under iron deficiency than Desferriverbindun- and form the iron binding brown-red complexes formed by a broad absorption band with a ma- ximum between 420 - 440 nm are characterized. Siderochrome by fungi and actinomycetes are Trihydroxamate.

The crude Siderochrome be isolated as follows: To 500 ml of culture filtrate 5 ml FeCl3 solution (1 00 mg / 1) to give, saturated with solid NaCl, 1/5 of the volume of chloroform-phenol (1: 1, V: G) extract , 20 min centrifugation at 3000 U / min, filter the organic phase, dilute with 2 vol. ether contaminated with Was¬ ser and lyophilize.

The Ferricrocinproduktion can be increased when a mutation of the Ferricrocinaufnahmesystems has set, the strains are auxotrophic arginine, ornithine δ-transaminase mu¬ advantage and / or the α-ketoglutarate dehydrogenase (lysine auxotrophy) is altered. An optimization of the production is achieved with glucose as carbon source (8 g C / l) and asparagine as N-Quelie (1 g N / 1). Here could be won * h over 60 hours [Kappner 10 mg l \: desferrinordanoxamine-Ferricrocinproduktion in Aspergillus viridi-nutans. Ducker and Thrower, Dissertation Tübingen, 1978)].

The compositions of the invention are placed in a conventional immersion bath, in which the will appears to einge¬ entrostenden surfaces. By means of a stirring or circulation system to be brought into intimate contact with the surface. Thus, the surface renewal rate can be kept high. Using a simple screen system means the bathroom zurückge¬ be maintained. According to one of the grate thickness - making depending on the applicational example in wire drawing, hot dip galvanizing, electroplating or painting - dependent residence time, the baths are filtered, concentrated, the agent, admixed with chelating agents and thereby separating released iron.

After separation of chelators and means the funds will be used How-of their duties according to the invention, and concentrated the chelators for the next processing. The work-up can be done externally.

The agents may according to the invention zen by brushing or spraying or whale be applied to the surfaces. After an exposure time of for example 5 minutes, they are by means of spraying or dipping, optionally also removed from the surface and wiping as described above, according to tätserschöpfung Kapazi¬ regenerated.

The invention also provides the process, the above-organisms Mi¬ little or no risk level that have extrazellu¬-cellular products with high iron binding capacity to enter directly into the pickling bath and to grow. Working up is analogous to the above statements.

Claims

Means for rust removal of surface organic-based as well as its preparation and application patent claims
1 . Means for rust removal of surfaces, characterized in that it two- of organic compounds with high affinity and / or trivalent iron is-products from biomass and in accordance with the known methods of recovering intracellular and extracellular Pro¬ recovered and by dipping or coating the grate fitting ¬ facing surfaces is used.
2. Composition according to claim 1, characterized in that the organi¬ specific component has a high iron binding capacity.
3. Means according to claims 1 and 2, characterized in that it is chelating siderophores, chromatophore, very all¬ common proteins, such as ferritin or other in Zel¬ len occurring organic compounds with high affinity for iron is ,
4. Means according to claims 1 and 3, characterized in that it passes ser immobilized for use on spherical carrier having up to 3 mm Durchmes¬.
5. A method for preparing an agent according to the aforementioned An¬ sayings, characterized in that suitable microorganisms for the production of the active components according to claim 3 are grown in almost iron-free culture media.
6. A method for microbial rust removal according to claims 1 to 5, characterized in that the means placed in a dipping bath in concentrations of 1 g / l and more.
7. Apparatus for carrying out the method according to th vorgenann¬ claims, characterized in that the means are brought relatively beizustand to the surfaces in a WIR via stirring or Umwälzaniagen and are retained on zu¬ screening systems in the immersion bath.
8. A process for mlkrobiellen rust removal according to claims 1 to 5, characterized in that the means on the workpiece supported auf¬ and rule by Wi¬ after a contact time of 5 minutes or dipping be removed again in a rinsing bath.
9. A process for the microbial rust removal according to claims 1 to 8, characterized in that the used agent through a membrane separation system with specific retention in dependence separated from the carrier material from the dip solution and are brought into contact with chelators that the iron from the medium release, and the regenerated agent be restored to their object, according while the iron ions aufkon¬ be centered separately.
1 0. A process for the microbial rust removal according to claims 1 to 3, characterized in that the suitable microorganisms used directly in the conventional Entrostungsbad and grown entspre¬ accordingly optimal conditions therein and be treated in the same claim. 9
PCT/EP1995/003670 1994-09-20 1995-09-18 Organically-based agent for removing rust from surfaces, production and use of said agent WO1996009423A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE19944433376 DE4433376C1 (en) 1994-09-20 1994-09-20 A method for removing rust from surfaces on an organic basis and process for producing the agent used
DEP4433376.5 1994-09-20

Publications (1)

Publication Number Publication Date
WO1996009423A1 true true WO1996009423A1 (en) 1996-03-28

Family

ID=6528611

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/003670 WO1996009423A1 (en) 1994-09-20 1995-09-18 Organically-based agent for removing rust from surfaces, production and use of said agent

Country Status (2)

Country Link
DE (1) DE4433376C1 (en)
WO (1) WO1996009423A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007015085A1 (en) * 2007-03-29 2008-10-02 Asa Spezialenzyme Gmbh A process for the removal of corrosion layers
US7759113B2 (en) 1999-04-30 2010-07-20 The General Hospital Corporation Fabrication of tissue lamina using microfabricated two-dimensional molds
US8173361B2 (en) 2003-01-16 2012-05-08 The General Hospital Corporation Method of determining metabolism of a test agent
US8491561B2 (en) 2002-03-25 2013-07-23 The Charles Stark Draper Laboratory Micromachined bilayer unit of engineered tissues

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19830848A1 (en) * 1998-07-10 2000-01-13 Daimler Chrysler Ag Methods and means for treating the surfaces of commodities
DE102007008655A1 (en) 2007-02-20 2008-08-21 Henkel Ag & Co. Kgaa Siderophore-metal complexes as bleaching catalysts,

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE352580A (en) *
US3110679A (en) * 1959-03-17 1963-11-12 Rubin Martin Neutral composition for removal of rust
FR2160464A1 (en) * 1971-11-16 1973-06-29 Kansai Paint Co Ltd
FR2219984A1 (en) * 1973-03-01 1974-09-27 Kansai Paint Co Ltd
JPS59113185A (en) * 1982-12-17 1984-06-29 Tomoji Tanaka Surface treatment of metal without causing environmental pollution

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE352580A (en) *
US3110679A (en) * 1959-03-17 1963-11-12 Rubin Martin Neutral composition for removal of rust
FR2160464A1 (en) * 1971-11-16 1973-06-29 Kansai Paint Co Ltd
FR2219984A1 (en) * 1973-03-01 1974-09-27 Kansai Paint Co Ltd
JPS59113185A (en) * 1982-12-17 1984-06-29 Tomoji Tanaka Surface treatment of metal without causing environmental pollution

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 101, no. 18, 29 October 1984, Columbus, Ohio, US; abstract no. 155919j, TANAKA: "Nonpolluting steel surface treatment" page 239; *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7759113B2 (en) 1999-04-30 2010-07-20 The General Hospital Corporation Fabrication of tissue lamina using microfabricated two-dimensional molds
US8642336B2 (en) 1999-04-30 2014-02-04 The General Hospital Corporation Fabrication of vascularized tissue using microfabricated two-dimensional molds
US8491561B2 (en) 2002-03-25 2013-07-23 The Charles Stark Draper Laboratory Micromachined bilayer unit of engineered tissues
US8173361B2 (en) 2003-01-16 2012-05-08 The General Hospital Corporation Method of determining metabolism of a test agent
DE102007015085A1 (en) * 2007-03-29 2008-10-02 Asa Spezialenzyme Gmbh A process for the removal of corrosion layers

Also Published As

Publication number Publication date Type
DE4433376C1 (en) 1996-04-04 grant

Similar Documents

Publication Publication Date Title
Lin et al. Encystment and polymer production by Azotobacter vinelandii in the presence of β-hydroxybutyrate
Brown et al. Loss of sensitivity to EDTA by Pseudomonas aeruginosa grown under conditions of Mg-limitation
Loveless et al. The influence of metal ion concentrations and pH value on the growth of a Nitrosomonas strain isolated from activated sludge
Nourbakhsh et al. A comparative study of various biosorbents for removal of chromium (VI) ions from industrial waste waters
Kristensen et al. Decomposition of plant materials in marine sediment exposed to different electron acceptors (O2, NO3−, and SO42−), with emphasis on substrate origin, degradation kinetics, and the role of bioturbation
US6068711A (en) Method of increasing corrosion resistance of metals and alloys by treatment with rare earth elements
US5441648A (en) Separation of heavy metals from aqueous media
US4626416A (en) Insoluble chelating compositions
Galán et al. Anammox bacteria and the anaerobic oxidation of ammonium in the oxygen minimum zone off northern Chile
Nelson et al. Sulfide oxidation in marine sediments: geochemistry meets microbiology
Trevors et al. Cadmium transport, resistance, and toxicity in bacteria, algae, and fungi
Hassen et al. Effects of heavy metals on Pseudomonas aeruginosa and Bacillus thuringiensis
Morel et al. Marine Bioinorganic Chemistry: The
Fetzer et al. Sensitivity of methanogenic bacteria from paddy soil to oxygen and desiccation
Hamilton Sulphate-reducing bacteria and anaerobic corrosion
Mickelsen et al. Ability of Neisseria gonorrhoeae, Neisseria meningitidis, and commensal Neisseria species to obtain iron from lactoferrin.
Pontefract et al. THE METABOLISM OF YEAST SPORULATION: IV. CYTOLOGICAL AND PHYSIOLOGICAL CHANGES IN SPORULATING CELLS
Nielsen et al. Studies on the in situ physiology of Thiothrix spp. present in activated sludge
Stagg et al. The accumulation of copper in Platichthys flesus L. and its effects on plasma electrolyte concentrations
Blackwell et al. Metal cation uptake by yeast: a review
Ehrlich Bacteriology of manganese nodules II. Manganese oxidation by cell-free extract from a manganese nodule bacterium
Aller et al. The effect of biogenic irrigation intensity and solute exchange on diagenetic reaction rates in marine sediments
Lanyi 1 Classical and rapid identification methods for medically important bacteria
Tuovinen et al. Bacterial, chemical, and mineralogical characteristics of tubercles in distribution pipelines
Yang et al. Current understanding of multi‐species biofilms

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA CN CZ FI HU JP KP KR NO NZ PL RO RU SG SI SK US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase in:

Ref country code: CA