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WO2007032001A2 - Procede de preparation de composites d'argent-polymere par depot sonochimique - Google Patents

Procede de preparation de composites d'argent-polymere par depot sonochimique Download PDF

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Publication number
WO2007032001A2
WO2007032001A2 PCT/IL2006/001066 IL2006001066W WO2007032001A2 WO 2007032001 A2 WO2007032001 A2 WO 2007032001A2 IL 2006001066 W IL2006001066 W IL 2006001066W WO 2007032001 A2 WO2007032001 A2 WO 2007032001A2
Authority
WO
WIPO (PCT)
Prior art keywords
silver
nylon
polymer
polyol
solution
Prior art date
Application number
PCT/IL2006/001066
Other languages
English (en)
Other versions
WO2007032001A3 (fr
Inventor
Aharon Gedanken
Nina Perkas
Stanislav Dubinsky
Samuel Gazit
Ran Rotem
Original Assignee
Bar-Ilan University
Nilit 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 Bar-Ilan University, Nilit Ltd. filed Critical Bar-Ilan University
Publication of WO2007032001A2 publication Critical patent/WO2007032001A2/fr
Publication of WO2007032001A3 publication Critical patent/WO2007032001A3/fr

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Classifications

    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides

Definitions

  • the present invention relates to silver-polymer composites and, particularly, to their preparation by sonochemical deposition.
  • the medical device may be made of any suitable material, for example metals, including steel, aluminum and its alloys, latex, nylon, silicone, polyester, glass, ceramic, paper, cloth and other plastics and rubbers, and the coating is formed by physical vapour deposition, for example, coating of one or more antimicrobial metals on the medical device by vacuum evaporation, sputtering, magnetron sputtering or ion plating.
  • metals including steel, aluminum and its alloys, latex, nylon, silicone, polyester, glass, ceramic, paper, cloth and other plastics and rubbers
  • the coating is formed by physical vapour deposition, for example, coating of one or more antimicrobial metals on the medical device by vacuum evaporation, sputtering, magnetron sputtering or ion plating.
  • Examples of commercially available yarns containing silver as an antimicrobial agent include a sheath-core yarn having silver particles in the sheath, FossFiberTM with AgIONTM (Foss Manufacturing Company, Inc., N.H., US), that protects against a broad spectrum of odor-causing and destructive bacteria, mold and mildew, using the proven antimicrobial properties of silver and is said to maintain the efficacy of its antimicrobial protection for the longevity of the product, even withstanding multiple launderings.
  • silver-containing nanocomposite fibers In order to achieve the optimum antibacterial effect of silver-containing nanocomposite fibers, a proper concentration of silver ions must be available in the solution.
  • the number of silver ions released from silver nanocrystals is about 30 times less than the number of silver ions released from silver complexes, but silver nanocrystals exhibit a better antimicrobial performance with a faster bacterial killing curve.
  • Pure silver is known to have a positive influence on wound healing, while silver complexes show a negative effect on the wound healing process.
  • the principal requirements for silver-polymer composites are small dimension of silver nanoparticles, their regular shape, and uniform size distribution.
  • silver available at present for this purpose is in the form of silver powder (particle size about 20 micron) and colloidal silver (particle size 30 nano).
  • Sonochemistry is the application of ultrasound to chemical reactions and processes. Ultrasound is the part of the sonic spectrum which ranges from about 20 kHz to 10 MHz: the range from 20 kHz to around 1 MHz is used in sonochemistry whereas frequencies far above 1 MHz are used as medical and diagnostic ultrasound.
  • the origin of sonochemical effects in liquids is the phenomenon of acoustic cavitation.
  • Acoustical energy is mechanical energy i.e. it is not absorbed by molecules.
  • Ultrasound is transmitted through a medium via pressure waves by inducing vibrational motion of the molecules which alternately compress and stretch the molecular structure of the medium due to a time- varying pressure. Therefore, the distance among the molecules vary as the molecules oscillate around their mean position. If the intensity of ultrasound in a liquid is increased, a point is reached at which the intramolecular forces are not able to hold the molecular structure intact and, consequently, it breaks down and a cavity is formed. This cavity is called cavitation bubble as this process is called cavitation and the point where it starts cavitation threshold.
  • a bubble responds to the sound field in the liquid by expanding and contracting, i.e. it is excited by a time-varying pressure.
  • Sonochemical irradiation has been proven as an effective method for synthesis of nanophased materials as well as for deposition and insertion of nanoparticles on/into mesoporous and ceramic supports.
  • the reasons that chemical bonds are ruptured when ultrasound radiation passes through a liquid are the high temperature (5000 0 K) and pressures (600 atm) developed when the acoustic bubble collapses.
  • One of the many advantages of sonochemistry is its ability to coat or dope various nanoparticles onto or into ceramics and polymers.
  • a homogeneous dispersion of the nanoparticles on the substrate is achieved in one step.
  • nanoparticles of the desired product are formed and accelerated at a very high speed onto/into the surface or body of the polymer or ceramics via microjets or shock waves created when the bubble collapses near solid surfaces.
  • a large variety of nanoparticles have been coated and doped onto and into polymers using sonochemical method/ultrasound irradiation. The deposition was conducted using materials which were either dissolved or dispersed (not dissolved) in the irradiated solution.
  • sonochemical deposition can be utilized for coating silver nanoparticles onto polymers.
  • the present invention provides a method for preparation of silver-polymer composites, which comprises sonochemical deposition of silver nanoparticles onto the polymer.
  • the method is carried out by ultrasonic irradiation of a polyol solution of a silver salt containing the polymer.
  • the polymer that can be coated with silver nanoparticles according to the invention may be any water insoluble polymer such as, without being limited to, nylon, polyester, polycarbonate (PC), polymethyl methacrylate (PMMA), or polypropylene.
  • the polymer is nylon.
  • the Ag-polymer composites of the invention can be characterized as polymer pellets coated by Ag nanoparticles.
  • concentration of the silver nanoparticles in the Ag-coated polymer pellets is at least one order of magnitude higher than the concentration needed for an antibacterial effect.
  • the Ag-coated polymer pellets can be used as a "master-batch" for the production of antibacterial yarns, for example, by melt spinning processes.
  • the "master batch” obtained may be metered into an extruder alongside the main polymer stream at a controlled ratio, whereby the silver nanoparticles get thoroughly mixed with the main polymer stream to form a diluted Ag-polymer composite, containing the required concentration of Ag-based particles needed for an antibacterial effect.
  • the diluted Ag-polymer may then be used for the production of yarns which are then knitted into fabrics.
  • the Ag/nylon composite of the invention was unexpectedly found to be stable to many washing cycles, and thus the antimicrobial properties of the fabrics knitted from these Ag-nylon yarns will be maintained through the washings of the garments for a long period of time.
  • the present invention relates to Ag-polymers, preferably Ag-nylon, composites obtained by the method of the invention; to antibacterial Ag-polymers, preferably Ag-nylon, yarns spun therefrom; and to fabrics knitted from said yarns.
  • the antibacterial fibers/yarns manufactured from the Ag-polymer composites prepared by the method of the present invention may be used for any of the known uses for such antibacterial fibers/yarns.
  • the antibacterial fibers/yarns manufactured from the Ag-nylon composites can be used for different purposes such as, but not limited to, performance apparel, medical textiles, uniforms, home furnishings, bedding, baby diapers, underwear, socks, hats, table cloth, carpet, floor mat, cleaning products, blanket, bed sheet, automotive textiles, tooth brush, shoes., etc. All of the above examples may be in the form of knitted, woven or non-woven fabrics.
  • Fig. 1 is a photo depicting nylon chips before and after sonochemical coating with silver, and Ag/nylon fibers spun from the Ag/nylon composite.
  • Ag-polymer composites are obtained with the main desired requirements, namely, a small dimension, a regular shape, and a uniform size distribution of silver nanoparticles.
  • microjets that are created in the irradiated solution when the acoustic bubbles collapse near solid surfaces, as described in the background section hereinabove. These microjets throw the silver nanoparticles onto the nylon surface at such a speed that the collision, according to our interpretation, causes the melting of the substrate guaranteeing the imbedding of the silver nanoparticles in the polymer surface.
  • At-polymer composites and “Ag-coated polymer pellets” are used interchangeably to define polymer pellets coated with silver nanoparticles, prepared according to the method of the present invention.
  • the polyol that can be used according to the method of the present invention may be any suitable alcohol containing at least two hydroxyl groups, such as a diol, a triol, and the like.
  • the polyol is a diol that may be a small molecule such as ethylene glycol or propylene glycol or a polymer such as polyethylene glycol (PEG) 400.
  • the polyol is ethylene glycol.
  • the polyol solution may be a pure polyol solution as well as a solution of said polyol in any suitable polar solvent.
  • the polyol solution is an aqueous polyol solution wherein the water : polyol ratio is in a range of 10: 1 (v:v) to 1 :5 (v:v), preferably 9: 1 (v:v).
  • the silver salt used in the method of the present invention may be any suitable silver salt such as, without limitation, silver nitrate, silver acetate or silver perchlorate.
  • the concentration of silver ions in the polyol solution determines the final silver amount in the silver-nylon composites prepared; however, by increasing the silver ions concentration, larger and more aggregated silver nanoparticles are obtained.
  • the concentration of Ag ions is in a range of 0.02 M to 0.1 M 5 most preferably 0.02 M.
  • the temperature of the polyol solution during the method of the invention may be in a range of 15 0 C to 60 0 C, preferably 2O 0 C to 40 0 C, most preferably about 3O 0 C.
  • the duration of the ultrasonic irradiation according to the present invention may be up to 4 hours, preferably in a range of 1 hour to 3 hours, most preferably about 2 hours.
  • the efficiency of the ultrasonic irradiation may be in the range of 50% to 80%, preferably 70%.
  • the present invention relates to a method for the preparation of silver-nylon composites comprising placing nylon pellets in a solution of a silver salt in an aqueous solution of a polyol, irradiating the mixture with a high intensity ultrasound horn for about 2 hours, and washing and drying the resulting product to obtain the desired silver-nylon composite.
  • the silver salt may be silver nitrate, silver acetate or silver perchlorate and the polyol solution is preferably an aqueous solution of ethylene glycol.
  • the invention further relates to silver-polymer composites obtained by the method of the invention, particularly to silver-nylon composites obtained by the method as described above and to antibacterial silver-nylon yarns spun from said silver-nylon composites.
  • sonochemistry was employed for coating nanosilver particles on Nylon 6,6 chips, as shown in Example 1 hereinafter.
  • this Ag/nylon composite was stable to many washing cycles. It is worth mentioning that 80 'laundering' cycles did not reduce the amount of silver on the nylon surface, thus demonstrating the efficient deposition of the silver nanoparticles by the ultrasonic irradiation according to the invention.
  • the fabric knitted from this yarn showed excellent antimicrobial properties. It worked on both gram positive and gram negative bacteria, while not all commercially available additives work on both types of bacteria.
  • the Ag-Nylon composite obtained contained 1.0% wt of Ag (0) .
  • the silver nanoparticles of 50-100 nm were homogeneously distributed in the polymer.
  • the power of the sonicator used in all experiments was 1.5 kW, but the sonication efficiency was 60, 65, 70 or 75%.
  • the results obtained indicate that the optimal sonication efficiency was 70% and that a reaction duration longer that 2 hours did not increase the silver concentration in the Ag-nylon composite.
  • Ag-Nylon composites prepared as described in Example 1 hereinabove were used as a master-batch for the preparation of antibacterial silver-coated nylon fibers.
  • the Log Reduction test showed a reduction of bacterial counts by 4 logs after 18 hours, both for gram positive ⁇ Staphylococus aureus) and for gram negative (Pseudomonas aeruginosa) bacteria.
  • Fig. 1 is a photo depicting nylon chips before (left) and after sonochemical coating with silver (middle), and Ag/nylon fibers spun from the Ag/nylon composite (right).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un procédé de préparation de composites d'argent-polymère, qui comporte l'étape consistant à déposer, par des techniques sonochimiques, des nanoparticules d'argent sur le polymère, de préférence en soumettant à un rayonnement ultrasonore une solution de polyol d'un sel d'argent contenant le polymère. L'invention concerne de plus des composites d'Ag-polymère, de préférence d'Ag-nylon, obtenus par la mise en oeuvre du procédé de l'invention, des composés antibactériens d'Ag-polymère, de préférence d'Ag-nylon, des fils formés à partir de ces composés, et des tissus tissés à partir de ces fils.
PCT/IL2006/001066 2005-09-12 2006-09-12 Procede de preparation de composites d'argent-polymere par depot sonochimique WO2007032001A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US71560905P 2005-09-12 2005-09-12
US60/715,609 2005-09-12

Publications (2)

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WO2007032001A2 true WO2007032001A2 (fr) 2007-03-22
WO2007032001A3 WO2007032001A3 (fr) 2007-06-14

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013160898A1 (fr) * 2012-04-24 2013-10-31 Argaman Technologies Ltd. Procédé pour l'application en surface de composés chimiques sur des fibres aussi bien synthétiques que naturelles et système correspondant
US9315937B2 (en) 2008-06-30 2016-04-19 Bar-Ilan University Sonochemical coating of textiles with metal oxide nanoparticles for antimicrobial fabrics
WO2017006259A1 (fr) * 2015-07-06 2017-01-12 Universita' Degli Studi Di Roma "Tor Vergata" Procédé pour la production de matériaux plastiques nanocomposites
ITUB20152019A1 (it) * 2015-07-08 2017-01-16 Fabrizio Quadrini Metodo di fabbricazione di additivi per plastiche nanocomposite con proprieta' antimicrobiche e antibatteriche
US10370789B2 (en) 2008-06-30 2019-08-06 Bar Ilan University Sonochemical coating of textiles with metal oxide nanoparticles for antimicrobial fabrics
EP3714090A1 (fr) * 2018-12-18 2020-09-30 Ascend Performance Materials Operations LLC Polyamides non tissés antimicrobiens à teneur en zinc
CN112839688A (zh) * 2018-09-14 2021-05-25 奥索赛尔有限公司 涂布纳米颗粒的胶原植入物
WO2023213588A1 (fr) * 2022-05-02 2023-11-09 Sabic Global Technologies B.V. Composite polymère antimicrobien décoré de métal-glycérol

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5180402A (en) * 1990-05-08 1993-01-19 Toray Industries, Inc. Dyed synthetic fiber comprising silver-substituted zeolite and copper compound, and process for preparing same
US6726964B1 (en) * 2001-07-11 2004-04-27 G. Alan Thompson Ultrasonic process for autocatalytic deposition of metal on microparticulate

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9315937B2 (en) 2008-06-30 2016-04-19 Bar-Ilan University Sonochemical coating of textiles with metal oxide nanoparticles for antimicrobial fabrics
EP2294260B1 (fr) * 2008-06-30 2016-11-02 Bar-Ilan University Enduction par voie sonochimique de textiles avec des nanoparticules d oxydes métalliques pour tissus antimicrobiens
US10370789B2 (en) 2008-06-30 2019-08-06 Bar Ilan University Sonochemical coating of textiles with metal oxide nanoparticles for antimicrobial fabrics
WO2013160898A1 (fr) * 2012-04-24 2013-10-31 Argaman Technologies Ltd. Procédé pour l'application en surface de composés chimiques sur des fibres aussi bien synthétiques que naturelles et système correspondant
US9995002B2 (en) 2012-04-24 2018-06-12 Argaman Technologies Ltd. Method for the surface application of chemical compounds to both synthetic and natural fibers and a system for same
WO2017006259A1 (fr) * 2015-07-06 2017-01-12 Universita' Degli Studi Di Roma "Tor Vergata" Procédé pour la production de matériaux plastiques nanocomposites
US20180273714A1 (en) * 2015-07-06 2018-09-27 Universita' Degli Studi Di Roma "Tor Vergata" Method for the production of nanocomposite plastic materials
ITUB20152019A1 (it) * 2015-07-08 2017-01-16 Fabrizio Quadrini Metodo di fabbricazione di additivi per plastiche nanocomposite con proprieta' antimicrobiche e antibatteriche
CN112839688A (zh) * 2018-09-14 2021-05-25 奥索赛尔有限公司 涂布纳米颗粒的胶原植入物
JP2022500146A (ja) * 2018-09-14 2022-01-04 オーソセル・リミテッド ナノ粒子被覆コラーゲン移植物
EP3714090A1 (fr) * 2018-12-18 2020-09-30 Ascend Performance Materials Operations LLC Polyamides non tissés antimicrobiens à teneur en zinc
WO2023213588A1 (fr) * 2022-05-02 2023-11-09 Sabic Global Technologies B.V. Composite polymère antimicrobien décoré de métal-glycérol

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