WO2012059944A2 - Blue coloured aqueous dispersion of silver nanoparticles a process for preparation and compositions thereof - Google Patents
Blue coloured aqueous dispersion of silver nanoparticles a process for preparation and compositions thereof Download PDFInfo
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- WO2012059944A2 WO2012059944A2 PCT/IN2011/000758 IN2011000758W WO2012059944A2 WO 2012059944 A2 WO2012059944 A2 WO 2012059944A2 IN 2011000758 W IN2011000758 W IN 2011000758W WO 2012059944 A2 WO2012059944 A2 WO 2012059944A2
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0043—Preparation of sols containing elemental metal
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/08—Processes in which the treating agent is applied in powder or granular form
Definitions
- the present invention provides blue coloured aqueous dispersion of silver nanoparticles and process for preparation thereof.
- the present invention also provides compositions comprising blue coloured dispersion of silver nanoparticles.
- Nanosilver is a highly potent antimicrobial agent.
- the state-of-the-art antimicrobial finishes based on nano silver are yellow to dark brown in colour depending upon the silver concentration.
- these silver nanodispersions When these silver nanodispersions are applied to textile or polymeric substrates, it often results in poor aesthetics in terms of lower Whiteness Index or higher Yellowness Index, which is undesirable primarily for white and pale shade garments or substrates.
- MBC Minimum Bactericidal Concentration
- the dispersions of nanosilver based finishes available in prior art are non durable.
- the nanoparticles tend to agglomerate and settle down with time in the dispersion form giving poor shelf life.
- Several additives used for stabilizing these nanofinishes often impart still deeper colours to the nano dispersion making it undesirable.
- Chemical reduction method This involves the dissolution of silver salt into a solvent (aqueous or nonaqueous) and subsequent addition of a suitable reducing agent e. g. chemical reduction of silver ion in aqueous solutions or non-aqueous solutions (Maribel G. Guzman, Jean Dille, Stephan Godet , World Academy of Science, Engineering and Technology 43 2008; Zaheer Khan, Shaeel Ahmed Al-Thabaiti, Abdullah Yousif Obaid, A.O. Al-Youbi, Colloids and Surfaces B: Biointerfaces 82 (2011) 513-517; CHEN Yanming Li, CN1994633, ; Sun, Rong; Zhao, Tao; Yu, Shuhui; Du, Ruxu, CN 102085574).
- a suitable reducing agent e. g. chemical reduction of silver ion in aqueous solutions or non-aqueous solutions
- MW Microwave (MW)-assisted synthesis
- K J Sreeram, M Nidhin and B U Nair, Bull. Mater. Sci., Vol. 31, No. 7, Dec 2008, pp. 937-942 Microwave (MW)-assisted synthesis
- MW provides rapid and uniform heating of reagents, solvents, intermediates, and products. Fast heating accelerates the reduction of metal precursors and the nucleation of the metal cluster, resulting in small nanostructures.
- Electron irradiation is a new method of reduction of precursor in a solution to produce nanoparticles.
- Microemulsion method (Zhi Ya Ma, Dosi Dosev and Ian M Kennedy, Nanotechnology 20 (2009) 085608).
- Microemulsion consists of a ternary mixture of water, surfactant and oil or a quaternary mixture of water, surfactant, co-surfactant and oil.
- Different surfactant that is, different microemulsion system employed in the fabrication process, silver nanoparticles with different diameters or morphologies are obtained.
- top-down techniques use silver metal in its bulk form, then, mechanically reduce its size to the nanoscale via specialized methodologies such as lithography (Xiaoyu Zhang, Alyson V. Whitney, Jing Zhao, Erin M. Hicks, and Richard P. Van Duyne , Journal of Nanoscience and Nanotechnology Vol.6, 1-15, 2006,) and laser ablation (A. Pyatenko, K. Shimokawa, M. Yamaguchi.O. Nishimura, M. Suzuki Appl. Phys. A, 79, 803-806 (2004)).
- the antimicribial activity of silver nanoparticles may be evaluated either in dispersion form to give MBC/MIC values in ppm ⁇ g/ml of dispersion) or after application on substrates in % reduction of microbial growth for a given concentration of silver in ppm ( ⁇ /g of fabric) using standard methods such as AATCCIOO, ASTM E 2149.
- MBC Minimum Bactericidal Concentration
- MBC value of 12.5 to 100 ⁇ g/ml have been reported towards Staphylococcus aureus, methicillin-sensitive S. aureus (MSSA), and methicillin-resistant S. aureus (MRSA) were examined against commercially available nanosilver particles (5-10 nm particle size).
- the silver is a precious metal and its application at higher concentration is commercially undesirable. The result of such a high concentration application eventually gives the fabric yellow to brown tinge depending on concentration. Durability of the silver nanoparticle finish is also a concern. Silver nanoparticles tend to wash off during repeated washing. And if the Ag nanoparticles are used with binders, though wash durability improves to some extent, the maximum efficiency/antimicrobial activity of nanoparticles gets reduced due to hindrance of binder.
- nanosilver dispersion of colours other than yellow and brown such as blue or purple can be prepared using the knowledge available in prior art. This can be done either in a solvent (non aqueous) or water (aqueous) system. Most of the processes for different coloured silver dispersions have been prepared in non-aqueous media, which is toxic, not ecofriendly, expensive, and inappropriate for application on variety of substrates such as textile, sport goods, biomedical material, etc.
- UV spectrum of blue coloured colloids LLS 218 had three peaks related to the Plasmon bands created with triangular prisms. Also the particle size of silver nanoparticles was large in the range of 20 nm to 50 nm. Though antimicrobial activity of these colloids were not reported, based on other studies as reported above, it is likely that these colloids would be needed to be applied in large concentrations for effective antimicrobial activity due to their large particles size.
- the dispersion of nanosilver prepared in this prior art was also light sensitive and was stable for only a few months when stored in dark.
- the present invention solves the problems of yellowing of fabric and other substrates on application of nanosilver finishes, stability of the aqueous dispersion of nanosilver during storage, their application at low concentrations, and wash durability of nanosilver finish on application.
- the aqueous dispersion of silver nanoparticles of the present invention is blue in colour, has nanosilver particles of very small in size, and can combine the effect of antimicrobial finish and brightening/bluing agent used for brightening the white and pale coloured substrates. It shows 99.99% antimicrobial activity at very low concentrations, is easy to synthesize directly in aqueous media, and is stable on storage even at high temperature and/or in light.
- the dispersion stability of the nano silver particles of present invention is for 15 to 24 months.
- the particles provide wash durability after application on textile, binding with simple heat treatment at temperatures greater than 120 degree C (120 to 150 degree C) or with binders at room temperature.
- the particles and their dispersions have very high compatibility with binders and surfactants of various types.
- An objective of the present invention is to provide blue coloured aqueous dispersion of silver nanoparticles characterized with plasmonic peaks in the range 330 - 335 nm and 650-720 nm combined with missing plasmonic peaks in the range 390 to 410 nm and 410-500 nm in UV-Vis spectrum and with high molar extinction coefficient in the range of 10.1 to 15.7 raM 'cm "1 at wavelength of maximum absorption in the range 650-720 nm.
- Another object of the present invention is to provide a process for preparation of blue colored aqueous dispersion of silver nanoparticles directly from precursors in one step.
- Yet another object of the present invention is to provide composition comprising blue colored aqueous dispersion of silver nanoparticles of the present invention for use as anti microbial agents or finishes.
- the blue colored aqueous dispersion of the silver nanoparticles has majority of silver particles in the range of 0.5 nm to 6 nm (in equivalent diameter term) and suitable as antimicrobial finish and optical brightening/bluing agent used for brightening the white and pale coloured substrates and is stable on exposure to light and/or to high temperature.
- the present invention provides blue colored aqueous dispersion of silver nanoparticles which is very LLS 218 stable and very effective antimicrobial agent having characteristic feature of having plasmonic peaks in the range 330 - 335 nm and 650-720 nm combined with missing plasmonic peaks in the range 390 to 410 nm and 410-500 nm in UV-Vis spectrum, having high molar extinction coefficient in the range of 10.1 to 15.7 mM '1 cm '1 at wavelength of maximum absorption in the range 650-720 nm, the dispersion having silver nanoparticles of anisotropic shape with majority of particles (>65) having equivalent diameter in range of 0.5 to 6 nm and Minimum Bactericidal Concentration (MBC) lower than 0.10 ppm preferably in the range of 0.055-0.099 ppm.
- MBC Minimum Bactericidal Concentration
- the present invention also provides process for preparation of said aqueous dispersion.
- the process of the present invention comprises steps of adding a protecting agent to silver precursor solution, followed by addition of stabilizer and hydrogen peroxide.
- the temperature is raised followed by addition of a reducing agent, which leads to formation of blue coloured aqueous dispersion of silver nanoparticles directly from precursor.
- present invention provides compositions comprising blue coloured aqueous dispersion of silver nanoparticles produced by the method of present invention.
- Figure 1 Optical photograph of blue coloured aqueous dispersion of silver nanoparticles.
- SAXS Small Angle X-ray Diffraction
- Figure 3 UV- vis spectrum of blue coloured aqueous dispersion of silver nanoparticles prepared in Example 1 (a) as prepared and (b) after 15 months.
- the graph shows stability of dispersion for over 15 months.
- Figure 4 Blue coloured aqueous dispersion of silver nanoparticles (after 15 months) a) Particle size distribution by volume using DLS (b) Zeta potential. DLS shows composite hydrodynamic diameter of Ag particle and the protective agent.
- Figure 5 UV- vis spectrum of blue coloured aqueous dispersion of silver nanoparticles with 0.1 wt% SDS surfactant.
- SAXS Small Angle X-ray Diffraction
- Antimicrobial activity Percentage reduction of microbes of an antimicrobial agent at a particular concentration. It can be evaluated by different standard testing methods either qualitatively or quantitatively. For non leaching type of testing more preferred method is colony counting method e. g. AATCC 100, ASTM E-2149. For leaching type of testing more preferred method is zone of inhibition e.g. AATCC 47, AATCC 90 etc.
- MBC Minimum Bactericidal concentration
- Procedure to evaluate MBC of aqueous dispersion of Blue Ag nanoparticle It is done by AATCC 100 (colony counting method).
- the silver dispersions were diluted 50-1000 times with Luria broth solution, inoculated with the tested bacteria at a concentration of 10 5 to 10 6 CFU/mL.
- the minimum bactericidal concentration (MBC) was evaluated after 24 h of incubation at 37 °C. After 24 hours of incubation, the minimum particular Ag concentration was determined at which more than or equal to 99.9% bacteria were killed.
- Protective agent/stabilizer It is a material that prevents the nanoparticles in aggregating in dispersion (liquid media).
- Zeta Potential It is the potential difference between the dispersion medium (here water) and the stationary layer of fluid attached to the dispersed particle. It indicates the degree of repulsion between adjacent, similarly charged particles in a dispersion. Its units are mV.
- Stability of a dispersion is related to the time taken by the dispersed particles in a dispersing medium to agglomerate and settle down under gravity. This makes the dispersion inhomgeneous and can not be used for applications. Dispersion with higher stability takes longer time to settle down.
- Dynamic light scattering (DLS): It sometimes referred to as Photon Correlation Spectroscopy (PCS) or Quasi-Elastic Light Scattering (QELS), is a well-established technique for measuring the size of macromolecules and particles typically in the submicron region. Particles, emulsions and macromolecules in suspension undergo Brownian motion. This is the motion induced by the bombardment by solvent molecules that themselves are moving due to their thermal energy. If the particles or molecules are illuminated with a laser, the intensity of the scattered light fluctuates at a rate that is dependent upon the size of the particles. Analysis of these intensity fluctuations yields the velocity of the Brownian motion and hence the particle size using the Stokes-Einstein relationship (Malvern Instruments, technical note).
- the fundamental size distribution generated by DLS is an intensity distribution, and then, it is converted, using Mie theory (Malvern Instruments, technical note; Chem. Rev. 2007, 107, 4797-4862), to a volume distribution.
- Intensity graph is not a true representation of amount of particles, as scattering intensity of signal is proportional to diameter of particle.
- Hydrodynamic diameter It is the composite diameter of a particle (surrounded by different ions and protective agents) in liquid media. In general, true diameter of the particle is less than its hydrodynamic diameter.
- Blue coloured dispersion of silver nanoparticles is generally composed of truncated triangular or triangular nanoplates, which have active facets (111). It is believed that high-atom-density facets such as ⁇ 111 ⁇ favor the reactivity of silver and it is having direct interaction with the bacterial surface.
- blue coloured aqueous dispersion of silver nanoparticles having higher reactivity in comparison to other blue coloured particles/dispersions reported in the literature, has been developed using a new method of preparation and using different concentration of additives.
- This blue coloured aqueous dispersion of Ag nanoparticles has overcome the above-mentioned shortcomings of the antimicrobial nanofinishes based on prior art.
- the combination of characteristic features of the Blue coloured dispersion of silver nanoparticles of the present invention, which distinguishes it from the prior art, are (a) the smaller size of the silver particle (measured by Small angle X-ray Scattering(SAXS) to be less than 6 nm in diameter for majority (i.e.
- the coloured dispersion of Ag nanoparticles obtained by the process of the present invention is optionally mixed with surfactants and binders to yield even more effective compositions for antimicrobial finishing of textiles as evidenced by increase in molar extinction coefficient in the range of 14.1 - 19.0 mM "1 cm “1 and minimum bactericidal concentration (MBC) values lower than 0.09 ppm, more preferably in the range (0.055 to 0.01 ppm), for control of the growth of microbes and perspiration odors for a variety of substrates including textile materials such as cellulosics such as cotton, wool, silk, polyester, viscose, polypropylene, nylons, Lycra, acrylic etc, and blends thereof.
- surfactants and binders to yield even more effective compositions for antimicrobial finishing of textiles as evidenced by increase in molar extinction coefficient in the range of 14.1 - 19.0 mM "1 cm “1 and minimum bactericidal concentration (MBC) values lower than 0.09
- Blue coloured aqueous dispersion of silver nanoparticles of present invention can be applied during textiles manufacture, processing, finishing and printing of various forms of fibers, filaments, yarns, sewing threads, towels, knits & woven & non woven textile and apparel.
- Blue coloured aqueous dispersion of silver nanoparticles described in the present invention can be applied along with durable press and wrinkle free finishing systems.
- the wrinkle free systems include thermosetting resins such as dimethylol dihydroxy ethylene urea (DMDHEU) resins; Dimethyl dihydroxy ethylene urea (DMeDHEU) certain transition-metal complexes, along with catalysts used for LLS 218 resin curing, polyethylene emulsions, softeners etc.
- DMDHEU dimethylol dihydroxy ethylene urea
- DMeDHEU Dimethyl dihydroxy ethylene urea
- This cross linking of blue silver with resin system provides durability on apparel up to 50 washes at an application dosage level of 2% of the fabric weight.
- Blue coloured aqueous dispersion of silver nanoparticles described in the present invention also finds antimicrobial applications in many different textiles for the home, apparel, medical, military and industrial use.
- Non-limiting examples of such textiles are shape-wear, socks, mattress ticking, roller hand towels, dish towels, bed linen, upholstery, soft furnishings, curtains, boot and shoe linings, carpets and mats, innerwear, intimate apparel and underwear briefs, T-shirts, active and athletic wear, leisure wear, sleepwear, swimwear, suits, uniform fabric & work wear, knitwear, denims, trousers, women's' knee-highs, hosiery and leg wear.
- Blue coloured aqueous dispersion of silver nanoparticles described in the present invention can be incorporated into articles of clothing for antimicrobial applications in jackets, vests, headwear, footwear (toe caps, heels, insoles, uppers, etc.), gloves, scarves, socks and leggings, neck gaiters, tents, sheeting & bedding , coated fabrics (PV, Polyurethanes, Silicone & PVC), sportswear, bath rugs, luggage fabrics, sleeping bags & duvets, and hats.
- coated fabrics PV, Polyurethanes, Silicone & PVC
- sportswear bath rugs
- luggage fabrics sleeping bags & duvets, and hats.
- Textile auxiliaries include but are not limited to textile finishing agents, fabric conditioners, moisture management finishes, antistatic agents, nucleating agents, soil release agents, optical brightening agents, antioxidants, UV stabilizers, fillers, softeners, lubricants, curing accelerators, encapsulated fragrances, textile detergents, and the like for providing malodor control and antimicrobial properties. All of such additional materials are well known to those skilled in the art and are commercially available.
- Blue coloured aqueous dispersion of silver nanoparticles described in the present invention can be used in textile composite materials including but not limited to textile foot mattress composites. Textile accessories including but not limited to textile collar linings, shirt buttons jacket fiber fillers and jacket insulating materials. All of these benefit from the antimicrobial protection provided by Blue colored silver nanoparticles as described in the present invention.
- Blue coloured aqueous dispersion of silver nanoparticles described in the present invention can be used for textile recycling and waste recycling to avoid the malodor generated during recycling and to help avoid the spread of diseases which may arise during the recycling process.
- Blue colored aqueous dispersion of silver nanoparticles described in the present invention can be used in textile preservation, including protection from dampness of apparel in all textile fabrics including canvass fabrics.
- Aqueous dispersion of blue coloured silver nanoparticles described in the present invention can be incorporated into non-woven fabrics and usually added along with latex binders for various applications including but not limited to non woven air filters.
- Blue coloured aqueous dispersion of silver nanoparticles described in the present invention can be incorporated into a wide range of consumer goods products, for the purpose of bringing an additional antimicrobial effect, or a boosted freshness effect.
- consumer goods products for the purpose of bringing an additional antimicrobial effect, or a boosted freshness effect.
- examples of such products include but are not limited to washing detergents, whether in liquid, powder, tablet or gel form, or rinse conditioners or rinse additives whether dilute or concentrate in nature.
- laundry wash additives such as stain removal enhancement products.
- Blue colored aqueous dispersion of silver nanoparticles can LLS 218 also be incorporated into tumble drier sheets. Additionally, blue colored aqueous dispersion of silver nanoparticles can be incorporated into fabric sprays, both with and without additional fragrance.
- Blue coloured aqueous dispersion of silver nanoparticles described in the present invention can be incorporated into many household products to bring an additional antimicrobial benefit or a freshness enhancement. This includes but is not limited to cat litter, air fresheners, hard surface cleaners and sprays, and floor cleaners. Blue Silver can also be used to treat mops, wipes and cloths to prevent bacterial growth and to keep such substrates fresh.
- Blue coloured aqueous dispersion of silver nanoparticles described in the present invention can be used to enhance the antimicrobial properties of a broad range of paper based products, such as diapers, incontinence products, facial tissues, toilet tissues, wipes and kitchen towels.
- Blue coloured aqueous dispersion of silver nanoparticles described in the present invention can be incorporated into numerous personal care products, including but not limited to such products as deodorants, anti-perspirants, talcum powders, body lotions, hair shampoos, hair conditioners, shower gels, bar soaps, body lotions and moisturizers and shaving gels.
- Blue coloured aqueous dispersion of silver nanoparticles described in the present invention can be incorporated into air filters, which can be vehicle and aircraft cabin air filters, or room and building based air filters in homes, offices and hotels. Blue colored aqueous dispersion of silver nanoparticles incorporation ensures filter materials are resistant to bacterial and fungal growth.
- Blue coloured aqueous dispersion of silver nanoparticles described in the present invention can be incorporated into medical dressings such as wound care materials and burn dressings to suppress bacterial and fungal growth, and the related risk of infection, in materials used for wound care dressings and burn dressings.
- blue colored aqueous dispersion of silver nanoparticles can be utilized in medical-healthcare products such as medical/healthcare wipes possessing anti-microbial properties.
- An additional use for blue coloured aqueous dispersion of silver nanoparticles as described in the present invention is in paints, coatings and wood preservative products, where it acts as a preservative and also delivers antimicrobial properties to the products.
- Blue coloured aqueous dispersion of silver nanoparticles described in the present invention can be incorporated into products designed to repel or eradicate bedbugs, such as textile coverings and sprays.
- the textile coverings include but are not limited to mattress ticking, sheets and bed coverings, and mattress coverings.
- Blue coloured aqueous dispersion of silver nanoparticles described in the present invention can be incorporated into products designed to kill or repel lice. This can be incorporated into textiles, covering and sprays or gels. Non-limiting examples are hats, hair netting and caps, hair spray, hair gels and creams.
- Blue coloured aqueous dispersion of silver nanoparticles of present invention can provide residual protection against pests like microorganisms or insects, growth of bacteria and can kill existing bacteria on various surfaces.
- Blue coloured aqueous dispersion of silver nanoparticles of present invention is effective against formation of Bio films on various surfaces.
- the present invention provides blue colored aqueous dispersion of silver nanoparticles which is very stable and very effective antimicrobial agent having characteristic feature of having plasmonic peaks in the range 330 - 335 nm and 650-720 nm combined with missing plasmonic peaks in the range 390 to 410 nm and 410-500 nm in UV-Vis spectrum, having high molar extinction coefficient in the range of 10.1 to 15.7 mM “1 cm “1 at wavelength of maximum absorption in the range 650-720 nm, the dispersion having silver nanoparticles of anisotropic shape with majority of particles ((65- 95%)) having equivalent diameter in range of 0.5 to 6 nm (peak value 2.6 nm of more than 70%) and Minimum Bactericidal Concentration (MBC) lower than 0.10 ppm preferably in the range of 0.055-0.099 ppm.
- MBC Minimum Bactericidal Concentration
- the present invention also provides a process for preparation of blue coloured aqueous dispersion of silver nanoparticles, the process comprising the steps of
- step (ii) adding a stabilizer and hydrogen peroxide to the solution of step (i);
- step (iii) heating solution of step (ii) to a temperature in the range of 50 to 90 degree C;
- step (iv) reducing the solution of step (iii) with a reducing agent to obtain blue coloured aqueous dispersion of silver nanoparticles.
- the present invention also provides compositions comprising blue coloured aqueous dispersion of silver nanoparticles for various applications described above.
- the silver precursor is selected from a group consisting of silver nitrate, silver perchlorate, silver acetate, silver sulphate and silvertetraoxychlorate.
- the silver precursor is silver nitrate.
- the protecting agent is selected from a group consisting of poly(ethylene- diamine), sodium acetate, bis(p-sulfonatopheny)phenyl phosphine dipotassium dihydrate, polythene glycol, polyvinyl alcohol and polyvinyl pyrrolidone.
- the protecting agent is polyvinyl pyrrolidone.
- a stabilizer is selected from the group consisting of ethylenediammine tetra acetate salt, nitrilo acetic acid salt and trisodium citrate.
- a stabilizer is trisodium citrate.
- a surfactant is optionally added before step (iv).
- the surfactant is selected from the group consisting of anionic and non ionic surfactants including sodium dodecyl sulfate(SDS), polysorbates, sodium salts of polyacrylic acids, ethylenediammine tetra acetate salt, nitriloacetic acid salt and trisodium citrate and condensates of benzo sulphonic acids.
- anionic and non ionic surfactants including sodium dodecyl sulfate(SDS), polysorbates, sodium salts of polyacrylic acids, ethylenediammine tetra acetate salt, nitriloacetic acid salt and trisodium citrate and condensates of benzo sulphonic acids.
- SDS sodium dodecyl sulfate
- polysorbates sodium salts of polyacrylic acids
- ethylenediammine tetra acetate salt ethylenediammine tetra acetate salt
- nitriloacetic acid salt
- the surfactant is sodium dodecyl sulfate(SDS).
- the reducing agent is selected from the group consisting of ascorbic acid, sodium tri-sec-butylborohydrate, lithium aluminium hydride, potassium tri-sec-butyl borohydride, potassium triethylborohydride, sodium triacetoxy borohydride and sodium borohydride.
- the reducing agent is sodium borohydride.
- reaction mixture is heated in the range of 50 to 90°C preferably in the range of 60-65°C.
- the mole ratio of silver precursor to protective agent is in the range of 1:0.1 to 1: 100, preferably 1:1 to 1: 10, more preferably 1:1 to 1:5.
- the mole ratio of silver precursor to stabilizer ranges from 1 : 1 to 1: 100, preferably 1:1 to 1:50, more preferably 1:5 to 1:15.
- the mole ratio of silver precursor to reducing agent is in the range of 1:8.5 to 1:50 preferably 1:10 to 1:20.
- the mole ratio of silver precursor to hydrogen peroxide is in the range of 1:50 to 1:500, preferably 1:100 to 1:300.
- the mole ratio of silver precursor to surfactant is in the range of 1:0.5 to 1:350, preferably in the range of 1:5 to 1:50 of the mixture.
- the blue coloured aqueous dispersion of Ag nanoparticles obtained by the process of present invention is optionally mixed with surfactants and binders to yield effective compositions for antimicrobial finish for variety of substrates including textile material such as cellulosic, wool, silk, polyester and nylons etc.
- a composition made in water comprising 1 - 99 wt% of blue coloured aqueous dispersion of silver nanoparticles, 0.001 to 10 wt% preferably 0.01 to 1.0 wt% of a surfactant optionally with 0.1 to 10 wt of a binder of the final composition.
- a composition made in water comprising 1 - 99 wt% of blue coloured aqueous dispersion of silver nanoparticles with a binder in the range of 0.1 to 10 weight% of the final composition.
- the surfactant is selected from the group consisting of anionic and non ionic surfactants including sodium dodecyl sulfate (SDS), polysorbates, sodium salts of polyacrylic acids, and condensates of benzo sulphonic acids or a mixture of any two or more selected from the group.
- anionic and non ionic surfactants including sodium dodecyl sulfate (SDS), polysorbates, sodium salts of polyacrylic acids, and condensates of benzo sulphonic acids or a mixture of any two or more selected from the group.
- the surfactant is sodium dodecyl sulfate(SDS).
- the binder is selected from the group consisting of acrylic based binder, epichlorohydrin-bishexamethylenetriamine based binder, copolymer binder with maleic acid, epoxy based binders, polyurethane based, and polyester based resin binders.
- the binder is epichlorohydrin-bishexamethylenetriamine based binder.
- the minimum bacteriocidal concentration (MBC) of the composition is lower than 0.09 ppm (range 0.055 ppm to 0.01 ppm).
- the molar extinction coefficient of the composition is above 14 (mM-cm) "1 , preferably in the range 14.1- 19.0 (mM-cm) " '.
- compositions gives no yellowing effect when applied on cotton fabrics at 120 deg C - 150 deg C and gives whiteness index higher than the control fabric by 10 - 85% when applied on fabric at 30-100 deg C.
- the process of the present invention provides blue coloured aqueous dispersion of silver nanoparticles with quantitative yield, smaller size, better purity with respect to particle shape and size, absence of plasmonic bands in the wavelength range of 390-500 nm and high molar extinction coefficient with significantly better properties, such as higher stability to exposure to light and heat, higher dispersion stability with storage time, and better compatibility with various additives, higher antimicrobial activity at lower concentrations and higher fixation to polymeric substrates as compared to the processes and products of the prior art.
- the present invention also provides composition of blue coloured aqueous dispersion of silver nanoparticles.
- the aqueous composition comprises the blue coloured aqueous dispersions of silver nanoparticles as obtained above with a surfactant optionally with a binder, which gives even higher molar extinction coefficient, better dispersion stability, higher antimicrobial activity and higher fixation on substrate than the above mentioned composition without surfactant.
- the amount of blue coloured aqueous dispersion of silver nanoparticles in the compisition may vary in the range of 1 - 99 wt%, surfactants in the composition may vary in the range from 0.001 to 10 weight%, preferably 0.01 to 1 wt% and binder in the range 0.1 wt% to 10 wt%. of the final
- Example 1 1 wt% of blue coloured aqueous dispersion produced in Example 1 was taken in DI water. To this 0.1 wt% SDS was added and stirred well. Fabric dipped and padded with 80-100% expression (% weight of liquid based on the dry weight of fabric). Fabric was dried at 80 degree C for 5 min and cured at 150 degree C for 3 min to get durable antimicrobial finish with out binder.
- Example 1 1 wt% of blue coloured aqueous dispersion produced in Example 1 was taken in water. To this 0.5 wt% of SDS was added and mixed well. To this 1 wt% of Epichlorohydrin-bishexamethylenetriamine polymer based binder was added and mixed well by stirring at room temperature.
- the Fabric was dipped and padded using the mixture of Example 4 at an expression of 80-100%.
- the treated fabric was dried at room temperature to get durable antimicrobial finish.
- plasmonic peak between 410-500 nm indicating a substantially different shape and/or size than those reported for prisms of prior art.
- the mathematical modeling of the nanopartices has shown that occurrence of plasmonic peaks is highly associated with the shape and size of the nanoparticles (ref. Advanced Materials, 17, No. 4, February 23, (2005), By Gabriella S. Metraux and Chad A. Mirkin).
- the aqueous dispersions of silver nanoprisms of prior art show at least three and sometime four plasmonic bands in the range 300-350 nm, 390-410 nm, 410-500 nm and 650-700 nm.
- the Minimum bactericidal concentration (MBC) value for blue coloured aqueous dispersion of Ag nanoparticles is less than 0.1 ppm (in the range of 0.055-0.099 ppm) against S. aureus (gram positive bacteria).
- the product is highly stable even after 15 months of storage under standard room conditions (30-40 deg C) of tropical weather kept in normal diffused sunlight. This is supported by particle size analysis of blue coloured aqueous dispersion of silver nanoparticles at after 15 months of storage time ( Figures 4 (a) ). Particle size remains small for over 15 months.
- compositions of blue coloured aqueous dispersions of silver nanoparticles with surfactants such as SDS give molar extinction coefficient higher than 14.0 mM “1 cm " , more precisely, in the range of 14.1-19.0 (mM-cm) '1 ( Figure 5) indicating deagglomeration of blue nanoparticles to still smaller size.
- binders The blue coloured aqueous dispersion of Ag nanoparticles is compatible with several types of binders and shows better properties such as higher fixation and activity on application with binders on various substrates.
- the types of binders tested are:
- the difference in whiteness index value when compared with untreated fabric is ⁇ 3
- the material of present invention with surfactant gives 99.9% antimicrobial activity at an application of 0.1 ppm and a durability of up to 99.9% activity for up to 20 harsher washes (AATCC 61 II A).
- the product when applied at any concentration 1-100% gives no perceptible colour change to even lightly coloured substrates such as white textiles or pale shade dyed textiles.
- composition may be fixed without the use of optional binder by heat treating the padded fabric/substrates at temperatures greater than 120 deg C to give significantly higher wash fastness than that reported in S. No. 1 of Table 3 above.
- the aqueous dispersion of silver nanoparticles of the present invention is blue in colour, has majority of silver particles that are very small in size (in the rage 0.5-6 nm), and can combine the effect of antimicrobial finish and bluing/brightening agent used for brightening the white and pale coloured substrates.
- the dispersion stability of the silver nanoparticles of present invention is 15-24 months in normal room conditions.
- the silver particles provide wash durability after application on textile, binding with simple heat treatment at temperatures greater than 120 degree C or with binders at room temperature.
- the dispersion has very high compatibility with binders and surfactants of various types.
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CN201180052576.7A CN103200825B (en) | 2010-11-02 | 2011-11-02 | Blue water-based dispersion, its preparation method and the composition thereof of silver nano-grain |
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EP2371221A3 (en) * | 2010-03-31 | 2013-07-31 | Rohm and Haas Company | Antibacterial polymer emulsion and coating composition |
US8802154B2 (en) | 2010-08-27 | 2014-08-12 | Sienna Labs, Inc. | Thermal treatment of a pilosebaceous unit with nanoparticles |
WO2014198352A1 (en) * | 2013-06-10 | 2014-12-18 | Instytut Chemii Fizycznej Polskiej Akademii Nauk | Method for surface modification with nanocomposites, nanocomposite material and the use thereof |
WO2015049267A1 (en) * | 2013-10-01 | 2015-04-09 | B. Braun Surgical, S. A. | A modified surface capable of having bacteriostatic and bactericide activity, the method for obtaining it and use thereof |
US20150210865A1 (en) * | 2014-01-29 | 2015-07-30 | Parash Kalita | Combinatorial Materials Architecture and Process for Textiles and Related Applications |
EP3088334A2 (en) | 2015-04-30 | 2016-11-02 | International Flavors & Fragrances Inc. | Nano silver for neutralizing thermoplastic bag and shoe malodors |
US9572880B2 (en) | 2010-08-27 | 2017-02-21 | Sienna Biopharmaceuticals, Inc. | Ultrasound delivery of nanoparticles |
US10688126B2 (en) | 2012-10-11 | 2020-06-23 | Nanocomposix, Inc. | Silver nanoplate compositions and methods |
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GB2500126B (en) | 2017-10-18 |
AU2011324794B2 (en) | 2015-09-03 |
WO2012059944A4 (en) | 2012-08-23 |
AU2011324794A1 (en) | 2013-05-02 |
GB201307682D0 (en) | 2013-06-12 |
WO2012059944A3 (en) | 2012-06-28 |
CN103200825A (en) | 2013-07-10 |
GB2500126A (en) | 2013-09-11 |
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US9403995B2 (en) | 2016-08-02 |
US20140005295A1 (en) | 2014-01-02 |
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