WO2007035099A1 - Amidon modifie, solution aqueuse d'un amidon modifie et procede de pretraitement de surfaces en acier - Google Patents

Amidon modifie, solution aqueuse d'un amidon modifie et procede de pretraitement de surfaces en acier Download PDF

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Publication number
WO2007035099A1
WO2007035099A1 PCT/NL2006/050232 NL2006050232W WO2007035099A1 WO 2007035099 A1 WO2007035099 A1 WO 2007035099A1 NL 2006050232 W NL2006050232 W NL 2006050232W WO 2007035099 A1 WO2007035099 A1 WO 2007035099A1
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WIPO (PCT)
Prior art keywords
modified
monosaccharide unit
groups per
polysaccharide
per monosaccharide
Prior art date
Application number
PCT/NL2006/050232
Other languages
English (en)
Inventor
Hendrik Jacobus Arie Breur
Gerritdina Hendrika Van Geel-Schutten
Theodoor Maximiliaan Slaghek
Ingrid Karin Haaksman
Original Assignee
Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno
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Application filed by Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno filed Critical Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno
Priority to EP06799522A priority Critical patent/EP1943373A1/fr
Publication of WO2007035099A1 publication Critical patent/WO2007035099A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/18—Oxidised starch
    • C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised starch
    • 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
    • C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09D103/04—Starch derivatives
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173—Macromolecular compounds

Definitions

  • the invention relates to a process, a compound and a composition for pretreating metal surfaces, in particular steel, for the purpose of enhancing corrosion resistance of the metal surfaces and/or adhesion of organic and inorganic coatings to the metal surfaces.
  • US 1,365,760 describes a dispersion of borax in a dextrin solution as an anti- corrosive coating for meal surfaces.
  • EP-B 850988 discloses an aqueous dispersion of highly acetylated, caprolactone-grafted starch, which is applied to aluminium foil, and, after drying and hot-rolling, forms a protective film.
  • US 6,194,033 discloses a composition for anticorrosive treatment of steel sheets containing an aromatic dye, colloidal silica, a hydroxylated and carboxylated polymer and an organic solvent such as tetrahydrofuran.
  • the hydroxylated and carboxylated polymer is e.g. bisphenol epoxy resin, poly(vinyl butyral) or another synthetic resin; alginic acid and starch are mentioned among many other possible polymers, but are not preferred.
  • the use of dyes and organic solvents is a disadvantage of this treatment.
  • Unmodified or N- methylated chitosan in acid solution is proposed as an anticorrosive agent for steel are proposed in WO 01/21854.
  • EP-A 1078963 describes the use of an emulsion of pregelatinised starch or crosslinked starch and a vegetable oil or wax for the treatment of metal surfaces, especially of steel.
  • the resulting coating should facilitates the subsequent moulding process and provide an temporary anticorrosive effect. It is shown that starch alone does not provide corrosion resistance, and even accelerates corrosion.
  • US 6,508,958 presents a process for protecting aluminium surfaces against corrosion by applying a solution of an acid-modified chitosan.
  • the chitosan is modified with polyfunctional acids such as aminotris(methylphosphonic acid) or adipic acid, so as to bridge chitosan strands and to hydrophobise the chitosan.
  • the alternatives summarised above have not shown to be satisfactory in terms of both anticorrosive performance, acceptable cost and health and environmental safety. Hence, there is still a strong need for novel and improved means and methods for anticorrosive treatments of metal sheets.
  • the polysaccharide to be used according to the invention can be any polysaccharide having repeating anhydroglycose units or their derivatives such as deoxy- anhydroglycose or anhydroglycuronic acid units.
  • Examples are glucans, galactans, mannans, glucomannans, galactomannans, fructans, arabans, xylans, arabinoxylans, arabinogalactans, etc.
  • the polysaccharide is a glucan, which may be either an ⁇ -glucan (starch family etc.), or a ⁇ -glucan or xyloglucan (cellulose and chitin, tamarind kernel, ⁇ -1,3 and/or ⁇ -1,6 glucans such as curdlan and scleroglucan).
  • ⁇ -glucans including starch, amylose, amylopectin, pullulan, nigeran, dextran, mutan, alternan, reuteran, and other ⁇ -1,3-, ⁇ - 1,4- and/or ⁇ -l,6-linked glucans.
  • starch which may be from any source, including potato, corn, rice, tapioca, etc.
  • the starch Prior to its oxidation, the starch is preferably gelatinised in a manner known per se, such as heat treatment in water at 60°C, or treatment with alkali.
  • the modified polysaccharide should have a molecular weight of at least 30 kDa (DP, degree of polymerisation of about 180), and the molecular weight may be as high as 10 MDa (DP about 60,000) or even higher.
  • the average molecular weight is at least 100 kDa or even 200 kDa, up to 3 MDa, or especially 1 MDa; the most preferred molecular weight is between 300 and 800 kDa (DP between about 1,800 and 5,000).
  • the molecular weight of a polysaccharide can be reduced by chemical treatment, such as hydrolysis, prior to or after modification, or even during modification by adapting the modification conditions (e.g. the temperature and/or pH during oxidation).
  • the modified polysaccharide contains from 0.1 to 0.9 anionic groups per mono- saccharide unit, preferably between 0.15 and 0.5 anionic groups per unit.
  • the anionic groups may be derived from carboxylic, phosphoric, sulphuric acid, and the like groups.
  • the acid groups can be present as a result of substitution or addition of suitable acid- containing reagents.
  • carboxylic groups may result from carboxyalkylation, in particular carboxymethylation, or from reaction with an anhydride such as maleic or succinic anhydride.
  • Phosphonic groups may be present as phosphate groups, resulting e.g. from reaction with phosphorylating agents (see e.g.
  • WO 97/28298 or as phosphonic or phosphinic acid groups, resulting e.g. from reaction with halomethyl phosphonic acids.
  • Sulphonic acids may be present e.g. as sulphate groups or as a result of sulphite addition to polysaccharide aldehydes (see e.g. WO 99/29354) or to maleic anhydride adducts (products with -0-CO-CH-CH(COOH)-SO 3 H groups).
  • the anionic groups are carboxylic groups resulting from oxidation, e.g.
  • the anionic groups are the ionised (salt) from, e.g. as alkali metal, alkaline earth metal, other metal, or ammonium salts.
  • the anionic groups stem from TEMPO-mediated oxidation of hydroxymethyl groups.
  • TEMPO-mediated oxidation is well documented in the art, see e.g. De Nooy, Synthesis 1996, 1153-1174, WO 95/07303, WO 00/50388, WO 00/- 50621, WO 01/00681, WO 02/48197 and. EP 1149846.
  • oxidising agent such as hypochlorite, hypobromite, hydrogen peroxide, or a peracid, or even oxygen
  • TEMPO 2,2,6,6-tetramethylpiperidine-N-oxyl
  • mediators such as halide ions, metal complexes or oxidative enzymes (e.g. peroxidase or phenol oxidase or laccase), leading to 6-carboxylic acid derivatives (uronic acids) in glucans and other aldohexose polymers.
  • a catalytic amount of nitroxyl is preferably 0.05-5% by weight, based on dry starch, or 0.05-5 mol% with respect to dry starch. Most preferably, these catalytic amounts are between 0.1 and 1 %.
  • the oxidation can be performed in aqueous solution or dispersion, e.g. by first adding TEMPO and optionally further catalysts or mediators, and then gradually or at once adding the oxidising agent, such a sodium hypochlorite solution, and reacting at temperatures between 0 and 50°C, preferably between 10 and 30°C, while maintaining neutral to mildly alkaline conditions, especially at a pH between 6 and 11, depending on the particular oxidising agent, preferably between 8 and 9.5.
  • the degree of oxidation determines the proportion of carboxyl groups in the modified polysaccharide, and can be varied by adapting the amount of oxidising agent. Any aldehyde groups remaining after oxidation may be further oxidised to carboxyl groups using additional of other oxidising agents, such as chlorite. [0014] It was found that improved efficacy is achieved when a part of the remaining hydroxyl groups of the anionic polysaccharide are hydrophobised by etherification or esterification. Etherification can be effected in a manner known per se, e.g.
  • C I -C O alkyl groups by reaction of the polysaccharide with the appropriate alkyl halide, sulphate or sulphonate, for example methyl iodide or diethyl sulphate. Esterification can be done with activated Ci-Cs monocarboxylic acids, such as acid halides or anhydrides of Ci -C O alkanoic, C3-C8 cycloalkanoic or C 7 -Cs benzoic or substituted benzoic acids. C2-C4 acyl groups are preferred.
  • the total degree of substitution (DS) of alkyl and acyl groups, preferably with acyl groups, is from 0.08 to 2.2 per monosaccharide unit.
  • Such a combination may e.g. be a methyl or ethyl group and an acetyl or propionyl group, an acetyl group and a propionyl or butyryl group, or a propionyl group and a buryryl group.
  • the ratio between the two different groups is preferably between 1:4 and 4:1, each accounting e.g. for 0.04 to 1.1 , especially from 0.2 to 1.0 group per monosaccharide unit.
  • the etherification and/or esterification can be carried out before or after the introduction of anionic groups.
  • the alkylation or acylation can be performed at the same conditions as most oxidation reactions, i.e. ambient temperature, a pH between 7 and 10, and in aqueous solution, preferably at relatively high concentration (e.g. between 5 and 75% wt.% of dry substance of the reaction mixture).
  • the invention furthermore pertains to modified glucans as such, which are modified in such a manner to contain from 0.1 to 0.9 carboxyl groups per monosaccharide unit, and from 0.1 to 1.0 acetyl groups and from 0.1 to 1.0 C3-C 4 alkanoyl and/or C 2 -C 4 alkyl groups per monosaccharide unit, the modified glucan having an average molecular weight of between 30 kDa and 10 MDa.
  • the invention also pertains to an aqueous solution of a modified polysaccharide containing from 0.1 to 0.9 anionic groups per monosaccharide unit and from 0.1 to 2.0 C1-C6 alkyl or alkanoyl groups, especially alkanoyl groups per monosaccharide unit, which is obtainable as described above.
  • the aqueous solutions can be used for treating metal surfaces
  • the aqueous solutions preferably have a dry substance content of between 0.3 and 6 wt.%, more preferably between 1 and 3 wt.%.
  • the pre-treatment solutions according to the invention can contain further components for stabilising the pre-treatment solution and for optimising the anticorrosive effect, such as lubricants, surfactants, other anti-corrosive agents, etc.
  • metal-containing anticorrosive agents may additionally be present, it is preferred that the pre-treatment solution of the invention has low levels of heavy metals (heavy meaning atomically heavier than calcium).
  • the weight ratio between any heavy metals and modified polysaccharide is below 0.1, preferably below 0.02.
  • the modified polysaccharides and their solutions can be used for pretreating metal sheets so as to increase their corrosion resistance and to enhance the adhesion of subsequently applied coatings.
  • the polysaccharides can furthermore be used as additives for other pre-treatment solutions such as in phosphating conversion coatings.
  • the metal sheets may advantageously be steel sheets, or surface-plated steel, such as tin-coated steel, galvanised steel or other metal-treated steel, or non-ferrous alloys such as aluminium.
  • the sheets can have any commercial shape and sizes.
  • the thickness is e.g. between 0.2 mm and 5 mm and the density, in case of steel, will typically be between 7 and 40 kg/m 2 .
  • the metal surface may undergo several treatments such as alkaline cleaning or acid pickling.
  • the sheets, after rolling and optional prior treatments and connected with a positive electric potential source, can be dip-coated in the solution for several seconds to several minutes, e.g. between 15 seconds and 2 minutes at ambient temperature to about 90°C, and then dried.
  • the potential is preferably -0.5 to -0.1 V (vs. saturated Ag/AgCl reference electrode) maintained during the coating stage.
  • the amount of modified polysaccharide coated onto the sheets is preferably between 0.1 and 15 kg/m 2 , more preferably between 0.5 and 5 kg/m (dry weight).
  • the resulting treated sheets have a protective layer which provides an improved corrosion resistance, which can be measured using conventional anodic polarisation scan in a salt solution, and increased adhesion of subsequently applied coatings or foils.
  • the invention also concerns metal sheets coated with a layer of polysaccharide as described above, which is modified to contain from 0.1 to 0.9 anionic groups per monosaccharide unit and from 0.1 to 2.0 C I -C O alkyl and/or alkanoyl groups per monosaccharide unit, the modified polysaccharide having an average molecular weight of between 30 kDa and 10 MDa.
  • the metal sheet is a steel sheet.
  • the metals sheets can be further processed and shaped to produce the desired semi-finished or finished products.
  • the metals sheets can e.g. be used in the automotive industry, aerospace industry, apparatus and utensils, building and construction industry etc.
  • Example 1 209 gram (1.3 mol) of partly (30%) C6-oxidised starch (obtained by TEMPO- mediated hypochlorite oxidation of gelatinised potato starch) was dissolved in 3 liter of demineralised water. A mixture of 267 gram (2.6 mol) acetic anhydride and 355 gram (2.6 mol) propionic anhydride was added dropwise during 4 hours. During the reaction, the pH was maintained at 8 by using a pH stat and 2 M NaOH, and the temperature was kept between 25 and 30 0 C. A precipitate was formed, which was separated by filtration. The residue (200 g) was mixed with 1 liter water to form a suspension, which was then cooled and freeze-dried.
  • the degree of substitution was determined by pretreating a sample by dissolving in water for free acid analysis and in 0.5 M NaOH for total acid analysis.
  • the sample was analysed using HPLC (column Aminex HPX-87H 300 mm x 7.8 mm, eluent 0.01 M sulphuric acid, and RI detection) and the analysis showed a degree of acetyl substitution of 0.8 and degree of propionyl substitution of 0.8.
  • Degreased carbon steel plates (10x 10cm 2 ) were subjected to a Galvanostatic deposition process in a medium containing 3.0 wt% NaCl and 0.1wt% of the modified starch at a current of 25 mA for 10 minutes.
  • OCP open cell potential
  • This measurement showed a black deposit settling on the surface.
  • the OCP showed an increase from -460 mV (vs. Ag/ AgCl reference electrode) towards -27OmV (vs Ag/ AgCl). This OCP increase is characteristic for a protective layer build-up. Without the addition of modified starch no stable deposit formation and no increase in potential were found.
  • Samples prepared with the modified starch according to example 3 were roll bar lacquered. The same process was carried out for panels without the treatment according to example 3. Adhesion of the coatings to the flat panels was tested using
  • Example 5 Samples prepared with the modified starch according to example 3 were roll bar lacquered. Subsequently, Electrochemical impedance spectroscopy (EIS) in 3 wt% NaCl medium was used to evaluate the relative corrosion resistance. For reference purposes, carbon steel panels were given the same coating treatment and were subjected to the same tests. From the data of the EIS measurements, it was clearly visible that the deposited layer showed active properties whereas this active behaviour was absent for the untreated sample. Furthermore, it was shown that contributions from the corrosion process, i.e. corrosion products and diffusion of corrosion products, were clearly more pronounced in the data for the not treated samples.
  • EIS Electrochemical impedance spectroscopy
  • Samples prepared with the modified starch according to example 3 were roll bar lacquered. For reference purposes, carbon steel panels were given the same coating treatment. Subsequently, an x-scribe was applied to all samples and scratched samples were exposed in 3 wt% NaCl medium. Visual observations showed that a without the treatment with modified starch, corrosion occurs rapidly, starting from the scribe. After 60 days, 90% of the surface showed corrosion or was even detached. For the samples with the modified starch treatment, slight detachment occurred during the same period and corrosion was present at 50% of the surface.

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

L'invention porte sur un procédé visant à renforcer la résistance à la corrosion de surfaces métalliques en traitant ces surfaces métalliques avec une solution aqueuse d'un polysaccharide modifié contenant de 0,1 à 0,9 groupes anioniques par unité de monosaccharide et de 0,1 à 2,0 groupes alkyle ou alcanoyle en C1-C6 par unité de monosaccharide. Le polysaccharide modifié a un poids moléculaire relativement élevé compris entre 30 kDa et 10 MDa.
PCT/NL2006/050232 2005-09-23 2006-09-22 Amidon modifie, solution aqueuse d'un amidon modifie et procede de pretraitement de surfaces en acier WO2007035099A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06799522A EP1943373A1 (fr) 2005-09-23 2006-09-22 Amidon modifie, solution aqueuse d'un amidon modifie et procede de pretraitement de surfaces en acier

Applications Claiming Priority (2)

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EP05108815.1 2005-09-23
EP05108815 2005-09-23

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WO2007035099A1 true WO2007035099A1 (fr) 2007-03-29

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10689566B2 (en) 2015-11-23 2020-06-23 Anavo Technologies, Llc Coated particles and methods of making and using the same
US10982013B2 (en) 2014-06-02 2021-04-20 Anavo Technologies, Llc Modified biopolymers and methods of producing and using the same

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0509202A1 (fr) * 1991-04-17 1992-10-21 Rheox International, Inc. Agents rhéologiques et épaissisants
JPH11310895A (ja) * 1998-04-28 1999-11-09 Sumitomo Metal Ind Ltd 亜鉛系電気めっき鋼板の製造方法
EP0999222A1 (fr) * 1998-11-02 2000-05-10 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Produits d'oxidation d'hydrates de carbone
EP1154074A1 (fr) * 2000-05-11 2001-11-14 SCA Hygiene Products Zeist B.V. Polymères contenant des aldéhydes, utilisés comme agents de résistance à l'état humide
WO2001090372A1 (fr) * 2000-05-25 2001-11-29 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Glucosyltransferase du lactobacillus reuteri
US20040112471A1 (en) * 2001-01-09 2004-06-17 Yoshio Moriya Aqueous surface conditioner and surface conditioning method for phospating treatment
US20050059633A1 (en) * 2001-07-20 2005-03-17 Van Geel-Schuten Gerritdina Hendrika Novel glucans and novel glucansucrases derived from lactic acid bacteria
EP1529820A1 (fr) * 2003-10-31 2005-05-11 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Liants à base de biopolymère
US20050106686A1 (en) * 2001-11-07 2005-05-19 Jetten Jan M. Process for oxidising dialdehyde polysaccharides

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0509202A1 (fr) * 1991-04-17 1992-10-21 Rheox International, Inc. Agents rhéologiques et épaissisants
JPH11310895A (ja) * 1998-04-28 1999-11-09 Sumitomo Metal Ind Ltd 亜鉛系電気めっき鋼板の製造方法
EP0999222A1 (fr) * 1998-11-02 2000-05-10 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Produits d'oxidation d'hydrates de carbone
EP1154074A1 (fr) * 2000-05-11 2001-11-14 SCA Hygiene Products Zeist B.V. Polymères contenant des aldéhydes, utilisés comme agents de résistance à l'état humide
WO2001090372A1 (fr) * 2000-05-25 2001-11-29 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Glucosyltransferase du lactobacillus reuteri
US20040112471A1 (en) * 2001-01-09 2004-06-17 Yoshio Moriya Aqueous surface conditioner and surface conditioning method for phospating treatment
US20050059633A1 (en) * 2001-07-20 2005-03-17 Van Geel-Schuten Gerritdina Hendrika Novel glucans and novel glucansucrases derived from lactic acid bacteria
US20050106686A1 (en) * 2001-11-07 2005-05-19 Jetten Jan M. Process for oxidising dialdehyde polysaccharides
EP1529820A1 (fr) * 2003-10-31 2005-05-11 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Liants à base de biopolymère

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Title
DATABASE WPI Section Ch Week 200011, Derwent World Patents Index; Class M11, AN 2000-119291, XP002369574 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10982013B2 (en) 2014-06-02 2021-04-20 Anavo Technologies, Llc Modified biopolymers and methods of producing and using the same
US10689566B2 (en) 2015-11-23 2020-06-23 Anavo Technologies, Llc Coated particles and methods of making and using the same

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