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WO2005068364A1 - Nano-argiles exfoliees - Google Patents

Nano-argiles exfoliees Download PDF

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Publication number
WO2005068364A1
WO2005068364A1 PCT/IN2004/000009 IN2004000009W WO2005068364A1 WO 2005068364 A1 WO2005068364 A1 WO 2005068364A1 IN 2004000009 W IN2004000009 W IN 2004000009W WO 2005068364 A1 WO2005068364 A1 WO 2005068364A1
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WO
WIPO (PCT)
Prior art keywords
clay
nanoclays
starch
organic compound
functional organic
Prior art date
Application number
PCT/IN2004/000009
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English (en)
Inventor
Sujit Banerji
Anand Kumar Kulshreshtha
Karumanchi Venkateswara Rao
Anil Vitthal Patil
Ajit Kumar Maiti
Sodagudi Francis Xavier
Original Assignee
Indian Petrochemicals Corporation Limited
Reliance Industries Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Indian Petrochemicals Corporation Limited, Reliance Industries Ltd. filed Critical Indian Petrochemicals Corporation Limited
Priority to PCT/IN2004/000009 priority Critical patent/WO2005068364A1/fr
Priority to DE112004002614T priority patent/DE112004002614T5/de
Publication of WO2005068364A1 publication Critical patent/WO2005068364A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material

Definitions

  • the present invention relates to intercalated layered materials. More particularly, the present invention relates to intercalated and exfoliated nanoclays. The present invention also relates to a method for the preparation of exfoliated nanoclays. More particularly, the present invention relates to a method for the preparation of exfoliated nanoclays by contracting and thereby intercalating, a polymer between and within platelets of mineral clay such as bentonite, by adsorption or flow. The resulting clay is filtered, dried and tested by X-ray diffraction. This results in producing exfoliated nanoclays from layered mineral clays.
  • the present invention relates to production of nanoclays for creating new markets for polymer nanocomposites from all types of plastics [biopolymers, thermoplastics, engineering plastics, thermosets, fibers, etc.] and boosting per capita consumption of plastic without posing any threat to environment.
  • Nanoclay is the latest layered clay for making plastics nanocomposites which have superior mechanical properties, barrier properties and flame resistance over conventional plastics and yet their optical properties remain intact because the addition level of nanoclay is in 1 to 6% range.
  • nanoclay In market the availability of nanoclay is very expensive [$55/Ib] and it is also marketed as masterbatches to mask its identity. This exorbitant cost is an ihibiting factor, which prevents widespread use of nanoclays in plastics and wider use of nanocomposites in many areas.
  • International companies, such as Polyone, Nanocor, RTP inc., Southern Clay Products inc., etc. are well known suppliers of nanoclys/masterbatches.
  • the purpose of this invention is to provide unrestricted availability of nanoclays to plastic producers and plastics processors-small as well as large-to create vast, untapped global markets for plastics. A decade ago nanocomposite technology was a concept with great potential. Today, it is a reality.
  • Nanoclays are surface modified montmorillonite minerals available for a range polymer resins from commodity polyolefins to specialty polyamides. Incorporation into these resins forms a nanocomposite plastic. Because Nanoclays are used at low addition levels, significant property improvement is achieved with lighter weight parts. Nanoclays have platey morphology .
  • the layered clays originated from volcanic ash. Common clays are naturally occurring minerals. The term “Bentonite” was applied for the first time to a particular kind of clay discovered near Fort Benton, Wyoming. This clay displays strong colloidal properties and when in contact with water, increases its volume several fold by swelling, giving rise to a thixotropic, gelatinous substance, but the other clay minerals such as illite and Kaolinite may be present.
  • the composition of montmorillonite [MMT ⁇ itself varies from one bentonite to another, but lies in the range of 75-95%.
  • Layered smectite- type MMT a hydrous alumina silicate mineral whose lamellae are constructed from octahedral alumina sheets sandwiched between two tetrahedral silicate sheets, exhibits a net negative charge on the lamellar surface, which enables them to adsorb cations, such as Na+ or Ca++.
  • Compatibility with various polymers is accomplished by modifying the silicates with alkylammonium cations via an ion exchange reaction [[Y.; Kurauchi T.T., Kamigaito, O.J Mater. Res.
  • the organic cations contain various functional groups that react with the polymers and reinforce adhesion between the particles and the matrix, thus producing nanocomposites with excellent dispersion quality in organic solvents.
  • the surfactant chain length gets larger, the charge density of the clay and the spacing between the clay layers increase.
  • shear any method which can be used to apply a shear to the intercalant/carrier composition can be used.
  • the shearing action can be provided by any appropriate method, as for example by mechanical means, by thermal shock, by pressure alternation, or by ultrasonics, all known in the art.
  • mechanical means such as stirrers, Banbury. RTM. Type mixers, long continuous mixers, and extruders.
  • AMCOL International Corporation has been active in seeking patent protection in this field and Nanocor is the beneficial holder of over two dozen US patents.
  • US 6,399,690 (2002) granted the above said company describes preparation of layered compositions with multicharged onium ions as exchange cations and their application to prepare intercalated and nanocomposites.
  • WO 97/31973 discloses producing a composite material by mixing potassium ionomer in which an ethylene methacrylate copolymer is either partially or completely neutralized with an organic polymer.
  • US Patent Nos. 4,739,007 and 5,164,460 disclose polyamide and polyimide composite materials respectively containing layered clay mineral intercalated with organic salts. In all the above patents, the intercalant were organic solvents. The organic pretreatment of the clay adds to the cost of the clay, even though the clay are relatively cheap. Need for intercalated and exfoliated clays has been growing as the field of Nanocomposites is at an embryonic stage of development today.
  • the present invention is carried out to fulfill the requirement for a cost effective intercalated [more preferably] bentonite clay and its nanocomposites there of with at least one polyolefine polymer such as polypropylene.
  • the composites disclosed in this invetion can be used for a myriad numbe of applications to biopolymers, thermosets, also such as furniture, automobile components, body parts, and parts left to the imagination of the moulder. Further, as described in Greenland, Adsorption of Polyvinyl Alcohols by Montmorillonite, Journal of Colloid Sciences, Vol 18, page 647-664 (1963), polyvinyl alcohols containing 12% residual acetyl groups could increase the basal spacing by only about 10. ANG.
  • a publication that discloses direct intercalation (without solvent) of polystyrene and Poly (ethylene oxide) in organically modified silicates is Synthesis and properties of Two dimensional Nanostructures by Direct Intercalation of Polymer Melts in Layered Silicates, Richard A. Vaia, et al. Chem. Mater., 5: 1694-1696 (1993). Also as disclosed in Adv. Materials, 7 No. 2: (1985), pp, 154-156, New Polymer Electrolyte Nanocomposites: Melt Intercalation of Poly (Ethylene Oxide) in Mica Type Silicates, Richard A.
  • Vaia, et al., poly (ethylene oxide) can be intercalated directly into Namontmorillonite and Li-montmorillonite by heating to 80°C. for 2-6 hours to achieve a d-spacing of 17.7 ANG.
  • the intercalation is accompanied by displacing water molecules, disposed between the clay platelets, with polymer molecules.
  • Intercalation Penetration of any chemical, monomer or polymer in between adjacent layers of clay.
  • Intercalation shall mean a process for forming an IntercalatE Exfoliation: Separation of clay layers resulting in their random dispersion.
  • Exfoliation shall mean a process for forming an Exfoliate from an Intercalate.
  • Exfoliate or “Exfoliated”: Individual platelets of an intercalated Layered Material so that the adjacent platelets of the Intercalated Layered Material can be dispersed individually throughout a carrier material, such as a matrix polymer.
  • Intercalant Polymer or "Intercalant”: An oligomer or polymer that is sorbed between Platelets of the Layered Material to form an Intercalant.
  • Bentonite A rock name given to the clay ore, which consists of smectite clay impurities such as gravel, shale and limestone
  • Smetite A mineral clay that has been the ability to swell in water. The most commercially important forms are hectorite and montmorillonite.
  • Montmorillonite The most available form of clay, classified as a magnesium silicate having a dioctahedral structure and a platy or sheet like morphology.
  • Cation A positively charged ion.
  • Gallery The spacing between parallel layers of montmorillonite clay platelets. The spacing changes depending upon which polymer or surface treatment occupies the space.
  • Intercalant An organic or semiorganic chemical capable of entering the smectite clay gallery and bonding to the surface.
  • Intercalate Treated clay that has a complex formed between the clay surface and an organic molecule.
  • Intercalate or “Intercalated” shall mean a Layered Material that includes oligomer and/or polymer molecules disposed between adjacent platelets of the Layered Material to increase the interlayer spacing between the adjacent platelets to at least 10 Angstroms.
  • Interlayer spacing Also known as the gallery.
  • Layered Material An inorganic material, such as a smectite clay, mineral, that is in the form of a plurality of adjacent, bound layers and has a maximum thickness, for each layer, of about 100 Angstroms.
  • Microx Polymer A thermoplastic or thermosetting polymer in which the Exfoliate is dispersed to form a Nanocomposite.
  • Nanocomposites A new class of plastics derived fro the incorporation of nanoscale particles into polymers.
  • Nanocomposite An oligomer, polymer or copolymer having dispersed therein a plurality of individual platelets obtained from an Exfoliated, Intercalated Layered Material.
  • X-Ray Diffraction It is also known as wide-angle- x ray scattering. It is one of the fundamental techniques of Materials Science. It gives a plot of scattered x-ray intensity as a function of scattering angle [two-theta]. XRD is used to determine crystal structure, crystallinity, crystal/amorphous ratio in polymers, metals, catalysts, adsorbents, etc. OBJECTS OF THE INVENTION It is an object of this invention to provide a process for the preparation of intercalated, preferably, exfoliated clay or more preferably, exfoliated bentonite clay of local origin for preparation of nanocomposites that is economical.
  • intercalates are prepared by contacting a phyllosilicate with a organic compound having an electrostatic functionality selected from the group consisting of a hydroxyl; a polyhdroxyl; an aromatic functionality; and mixtures thereof.
  • a swellable layered material that sufficiently sorbs the intercalant monomer to increase the interlayer spacing between adjacent phyllosilicate platelets to at least about 5.
  • A preferably to at least about 10.
  • A. (when the phyllosilicate is measured dry) may be used in the practice of this invention.
  • Useful swellable layered materials include phyllosilicates, such as smectite clay minerals, e.g., Montmorillonite, particularly sodium montmorillonite; mangsium montmorillonite and/or calcium montmorillonite; nontronite; beidellite; volkonskoite; hectorite; saponite; sauconite; sobockite; stevensite; svinfordite; vermiculite; and the like.
  • Other useful layered materials include micaceous minerals, such as illite and mixed layered illite/smectite minerals, such as rectorite, tarosovite, ledikite and admixtures of illites with the clay minerals named above.
  • Smectite clays contain absorbed molecular water (H 2 O), which is loosely held. Therefore, the hydrolysis process which occurs during weathering involves two kinds of hydrogen, bound as either as OH or H 2 O, which is found in two different types . of crystallographic site. Under laboratory or factory conditions the crystalline water is lost at higher temperatures than the absorbed interlayer water.
  • the present method makes use of water-friendly nature of clay and not its ion- exchange ability. A neutral hydrophilic molecule enters the gallery of clay and lies flat.
  • the organic compound having at least one of the above-defined functionalities, in a concentration of at least about 2% preferably at least about 5% by weight functional organic compound, more preferably about 30% to about 80% by weight, based on the weight of functional organic compound and carrier (e.g., water, with or without an organic solvent for the functional chemical compound) to achieve better sorption of the functional monomeric organic compound between phyllosilicate platelets.
  • functional organic compound and carrier e.g., water, with or without an organic solvent for the functional chemical compound
  • Figure 1 A comparison of the x-ray diffractograms of bentonite and nanoclay made by, modifying it [BIO-CLAY]; and Figure 2: shows a schematic representation of the process of the present invention.
  • Smectite clays can be intercalated sufficiently for subsequent exfoliation by sorption of polymers having carbonyl, carboxyl, hydroxyl amide, amine, phosphate or aromatic rings to provide complexing or bonding of the intercalant [chemical activator] to the inner platelet surfaces of the clay.
  • Water compatible or soluble or slurry forming polymers are chosen as intercalants for making nanoclay from layered silicate materials (clays). These can provide the necessary hydrogen bridge bonds between the hydroxyl groups of the platelets. Addition of polar substance attains delamination ["exfoliation”] by penetrating between the platelets forcing them apart by internal pressure. Application of shear forces may sometimes be necessary to achieve a complete exfoliation of clay into so- called nanoclay. In the present work, clay is interacted with an aqueous solution or suspension of a natural or modified polysachharide till its penetration and absorption reaches saturation. The carbohydrate penetrates between the platelets, forcing them apart. Application of shear completes the dispersion of nanoclay.
  • intercalation or exfoliation of treated clay is judged by the presence or absence of peaks in X-ray diffraction pattern or diffractogram.
  • Intercalated clay is not a nanoclay but is a precursor of it. When an intercalated clay is subjected to high shear in a twin -screw extruder, it gets exfoliated to different extents subject to degrees of applied shear. Exfoliated clay is the true nanoclay as it shows an amorphous, non-crystalline structure and does not probably need shear to disperse individual clay layers or platelets. In the X-ray diagrams, exfoliated clay shows a complete lack of diffraction peaks or a residual small, broad peak.
  • Figure 1 is an example of XRD of exfoliated nanoclay produced by an intercalation of carbohydrate molecule.
  • intercalated structures that are characterized by parallel registry give rise to X-ray peak at d-spacings in the range 20-30 A.
  • Bentonite is converted into exfoliated nanoclay by an ingenious scheme under which a mixture of various carbohydrate molecules slip layer-by-layer into the interlayer gallery. Once there, these molecules physically block bonding between adjacent clay layers thus preventing a recrystallization of clay ["exfoliation”]. Layers get dismantled.
  • Carbohydrate intercalants may be of natural origin or may have been synthetically modified.
  • Carbohydrates may be of plant or seaweed origin, e.g., potato, maize, rice or may belong to following molecular species: aligins, okra, industrial gum, pectins, mannans, amylopectins, amylosearabinoxylans, carrageenans, gum arabic, cellulouse, chitin, xanthan, galactoglucomannans, glycogens, polydextrose, agars, guar gum, cationic starches, wheat starch, tapioca starch, chitosans, oxidized starches, starch acetates/ phosphates/succinates, etc.
  • the viscosity obtained by cooking a suspension of starch is determined by the starch type, derivatization and/or modification, solids concentration, pH, amount of agitation during heating, rate of heating, maximum temperature reached, time held at that temperature, agitation during holding and presence of other ingredients.
  • An aqueous dispersion of an unmodified starch containing amylose will gradually form an insoluble precipitate through association of linear segments.
  • Bentonite clay is kept soaked in a [0-20%] solution or suspension of chosen carbohydrates in aqueous alcohol with alcohol content in the range 0-15% for a period 5- 25 hours. The clay thus modified is dried at the end of experiment to give an -ray silent spectrum of exfoliated nanoclay.
  • a phyllosilicate such as a smectite clay
  • a phyllosilicate can be intercalated sufficiently for subsequent exfoliation by sorption of organic compounds that have a hydroxyl or polyhydroxyl functionality; or at least one aromatic ring to provide bonding between two functional hydroxyl groups of one or two intercalant monomer molecules and the metal cations of the inner surfaces of the phyllosilicate platelets.
  • Sorption or bonding of a platelet metal cation between two hydroxyl groups of the intercalant organic molecules; or the bonding between the interlayer cations in hexagonal or pseudohexagonal rings of the smectite platelet layers and an intercalant monomer aromatic ring structure is provided by a mechanism selected from the group consisting of ionic complexing; electrosatic complexing; chelation; hydrogen bonding; dipole/dipole; Van Der Waals forces; and any combination thereof.
  • Such intercalated phyllosilicates can be easily exfoliated into individual phyllosilicate platelets before or during admixture with a liquid carrier, aqueous solution or solvent, for example, one or more monohydric alcohols, such as methanol, ethanol, propanol, and/or butanol; polyhydric alcohols, such as glycerols and glycols, e.g., ethylene glycol, propylene glycol, butylenes glycol, glycerine and mixtures thereof; aldehydes ketones; carboxylic acids; amines; amides; and other organic solvents.
  • a liquid carrier aqueous solution or solvent
  • aqueous solution or solvent for example, one or more monohydric alcohols, such as methanol, ethanol, propanol, and/or butanol; polyhydric alcohols, such as glycerols and glycols, e.g., ethylene glycol, propylene glycol,
  • the intercalates can be exfoliated and dispersed into one or more melt processible thermoplastic and/or thermosetting matrix oligomers or polymers, or mixtures thereof.
  • Matrix polymers for use in this embodiment of the process of this invention may vary widely, the only requirement is that they are melt processible.
  • the polymer includes at least-ten (10), preferably, at least thirty (30) recurring monomeric units.
  • the upper limit to the number of recurring monomer units is not critical, provided that the melt index of the matrix polymer under use conditions is such that the matrix polymer forms a flowable mixture.
  • the matrix polymer includes from at least about 10 to about 100 recurring monomeric units.
  • the number of recurring units is such that the matrix polymer has a melt index of from about 0.01 to about 12 grams per 10 minutes at the processing temperature.
  • Thermoplastic resins and rubbers for use as matrix polymers in the practice of this invention may vary widely.
  • thermoplastic resins which may be used alone or in admixture, are polyactones such a poly (pivalolactone), poly (caprolactone) and the like; polyurethanes derived from reaction of diisocyanates such as 1,5- naphthalene diisocyanate; p-phenylene diisocyanate, m-phenylene diisocyanate, 2,4-toluene diisocyanate, 4,4 '-diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3 '-dimethyl 4,4' biphenyl diisocyanate, 4,4'- diphenylisopropylidence diisocyanate, 3,3 '-dimethyl- 4'4'- diphenyl diisocyanate, 3,3,- dimethyl-4,4'- diphenylmethane diisocyanate, 3,3'-dimethoxy- 4,4'- biphenyl di
  • Example 1 to 3 Method of Preparation of Nanoclay
  • 10 gm rice was boiled in 1 litre of water. It was cooled and its solids concentration was measured and subsequently adjusted to 1%. About 25 gm of sodium bentonite clay, having a moisture of 20%, was kept in a 1 -litre beaker and a 250 ml of rice solution-cum- slurry was added to it .Another 250 ml of de-ionized water was added to beaker containing clay mass.
  • Nanoclay was ground to pass through 100-mesh sieve. Its x-ray diffractogram was taken to establish its exfoliation.
  • Example 2 0.1% aqueous glycerol solution, 125 ml was added to about 25 gm of sodium bentonite clay, having a moisture of 20%. Then it was stirred well to make mass homogeneous . The system was kept undisturbed for 1-2 days, after which it was dewatered by filtration and oven-dried at 90 °C, until it reached constant weight. Nanoclay was ground to pass through 100-mesh sieve.
  • Example 3 2% aqueous poly(vinyl alcohol) solution, 175 ml was added to about 25 gm of sodium bentonite clay having a moisture of 20%. Then it was stirred well to make mass homogeneous . The system was kept undisturbed for 1-2 days, after which it was dewatered by filtration and oven-dried at 90 °C, until it reached constant weight. Nanoclay was ground to pass through 100-mesh sieve. Its x-ray diffractogram was taken to establish its exfoliation.
  • Example 4 Preparation and Test Results of PP nanocomposites 6% of above clays and a commercial clay (Cloisite 20 A) were compounded in our company's 100 gm of polypropylene homopolymer powder having a MFI of 12, with 5% addition of MA-g-PP or a organo-silane. These were dry-mixed for 15 min at ambient temperature. The mixture was premixed for 3 min molded in DSM microcompounder and injection molder for 1 min. Mechanical property testing data for nanocomposites is given in table below :
  • tensile strength at break of indigenous nanoclay nanocomposite is 350% higher than that made from CLOISITE 20 A, although at about 20% reduction in impact strength.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des nano-argiles exfoliées et leur procédé de préparation à partir d'argiles smectiques ordinaires en couches [telles qu'une argile minérale bentonite de Gujarat]. Dans ce procédé, l'exfoliation se produit dans l'argile par insertion d'intercalants (substances chimiques/agents de gonflement/solvants/monomères/polymères). Ces intercalants peuvent former un composé avec l'argile et perturber la régularité d'organisation des couches. Ledit procédé permet d'obtenir des nano-argiles partiellement ou complètement exfoliées. Un nanocomposite de polypropylène peut être produit par utilisation d'une nano-argile bentonite exfoliée et de cloisite 20A. La résistance à la rupture d'un nanocomposite est 3,5 fois celle d'un nanocomposite commercial.
PCT/IN2004/000009 2004-01-13 2004-01-13 Nano-argiles exfoliees WO2005068364A1 (fr)

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DE112004002614T DE112004002614T5 (de) 2004-01-13 2004-01-13 Exfoliierte Nanolehme

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2277563A1 (es) * 2005-12-29 2007-07-01 Nanobiomatters, S.L. Procedimiento de fabricacion de materiales nanocompuestos para aplicaciones multisectoriales.
US7758691B2 (en) * 2004-09-09 2010-07-20 Herve Demais Intercalated clays
US20120112118A1 (en) * 2009-07-24 2012-05-10 Snur&Db Soundproofing Nanoclay Composite and Method of Manufacturing the Same
EP2597112A1 (fr) * 2011-11-25 2013-05-29 The Provost, Fellows, Foundation Scholars, & the other members of Board, of the College of the Holy & Undiv. Trinity of Queen Elizabeth near Dublin Procédé pour la production d'un produit composite par la combinaison d'un traitement en solution et en fusion
EP2674397A1 (fr) * 2012-06-15 2013-12-18 Olmix Procédé de préparation d'une argile organophile intercalée et/ou exfoliée à partir d'argile et de macroalgues, produit fertilisant, complément alimentaire pour animaux et aliment pour poisson correspondants
US9643889B1 (en) 2016-04-08 2017-05-09 King Saud University Method of storing exfoliated nanoclay particles
CN109205633A (zh) * 2018-08-31 2019-01-15 茂名市兴煌化工有限公司 一种新型纳米粘土制备系统
CN112794335A (zh) * 2021-01-14 2021-05-14 东北大学 一种用于阻隔的瓜尔胶改性膨润土及其制备方法
US11008442B2 (en) * 2007-06-01 2021-05-18 Plantic Technologies Ltd. Starch nanocomposite materials
CN115893914A (zh) * 2022-11-24 2023-04-04 龙岩市宝丽建材科技有限公司 一种外墙eps装饰线条用砂浆及其制备方法

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7758691B2 (en) * 2004-09-09 2010-07-20 Herve Demais Intercalated clays
WO2007074184A1 (fr) * 2005-12-29 2007-07-05 Nanobiomatters, S.L. Procede de fabrication de materiaux nanocomposites destines a des applications multisectorielles
ES2277563B1 (es) * 2005-12-29 2008-06-16 Nanobiomatters, S.L. Procedimiento de fabricacion de materiales nanocompuestos para aplicaciones multisectoriales.
RU2412114C2 (ru) * 2005-12-29 2011-02-20 Нанобиомэттерс, С.Л. Способ получения нанокомпозиционных материалов для применения во многих областях техники
ES2277563A1 (es) * 2005-12-29 2007-07-01 Nanobiomatters, S.L. Procedimiento de fabricacion de materiales nanocompuestos para aplicaciones multisectoriales.
US11008442B2 (en) * 2007-06-01 2021-05-18 Plantic Technologies Ltd. Starch nanocomposite materials
US11718733B2 (en) 2007-06-01 2023-08-08 Plantic Technologies Ltd. Starch nanocomposite materials
US20210246286A1 (en) * 2007-06-01 2021-08-12 Plantic Technologies Ltd. Starch Nanocomposite Materials
US20120112118A1 (en) * 2009-07-24 2012-05-10 Snur&Db Soundproofing Nanoclay Composite and Method of Manufacturing the Same
US8845917B2 (en) * 2009-07-24 2014-09-30 Snu R&Db Foundation Soundproofing nanoclay composite and method of manufacturing the same
EP2597112A1 (fr) * 2011-11-25 2013-05-29 The Provost, Fellows, Foundation Scholars, & the other members of Board, of the College of the Holy & Undiv. Trinity of Queen Elizabeth near Dublin Procédé pour la production d'un produit composite par la combinaison d'un traitement en solution et en fusion
WO2013076296A1 (fr) * 2011-11-25 2013-05-30 The Provost, Fellows, Foundation Scholars, & The Other Members Of Board, Of The College Of The Holy And Undiv. Trinity Of Queen Elizabeth, Near Dublin Procédé de production d'un produit composite par combinaison d'un traitement de solution et d'un traitement par fusion
FR2991978A1 (fr) * 2012-06-15 2013-12-20 Olmix Procede de preparation d'une argile organophile intercalee et/ou exfoliee a partir d'argile et de macroalgues, produit fertilisant, complement alimentaire pour animaux, aliment pour poisson et charge pour ceramique correspondants.
EP2674397B1 (fr) 2012-06-15 2017-08-23 Olmix Procédé de préparation d'une argile organophile intercalée et/ou exfoliée à partir d'argile et de macroalgues, produit fertilisant, complément alimentaire pour animaux et aliment pour poisson correspondants
WO2013186452A1 (fr) * 2012-06-15 2013-12-19 Olmix Procédé de préparation d'une argile organophile à partir d'argile et de macroalgues, produit fertilisant, complément alimentaire pour animaux, aliment pour poisson et charge pour céramique correspondants
EP2674397A1 (fr) * 2012-06-15 2013-12-18 Olmix Procédé de préparation d'une argile organophile intercalée et/ou exfoliée à partir d'argile et de macroalgues, produit fertilisant, complément alimentaire pour animaux et aliment pour poisson correspondants
US9643889B1 (en) 2016-04-08 2017-05-09 King Saud University Method of storing exfoliated nanoclay particles
CN109205633A (zh) * 2018-08-31 2019-01-15 茂名市兴煌化工有限公司 一种新型纳米粘土制备系统
CN109205633B (zh) * 2018-08-31 2023-09-22 林焕 一种新型纳米粘土制备系统
CN112794335A (zh) * 2021-01-14 2021-05-14 东北大学 一种用于阻隔的瓜尔胶改性膨润土及其制备方法
CN115893914A (zh) * 2022-11-24 2023-04-04 龙岩市宝丽建材科技有限公司 一种外墙eps装饰线条用砂浆及其制备方法

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