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WO2011106526A2 - Procédé de formation électrochimique de nanoparticules nobles dans une matrice de chitosane - Google Patents

Procédé de formation électrochimique de nanoparticules nobles dans une matrice de chitosane Download PDF

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Publication number
WO2011106526A2
WO2011106526A2 PCT/US2011/026075 US2011026075W WO2011106526A2 WO 2011106526 A2 WO2011106526 A2 WO 2011106526A2 US 2011026075 W US2011026075 W US 2011026075W WO 2011106526 A2 WO2011106526 A2 WO 2011106526A2
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WIPO (PCT)
Prior art keywords
chitosan
stainless steel
coating
layer
electrode
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Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2011/026075
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WO2011106526A3 (fr
Inventor
Gary Halada
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Research Foundation of the State University of New York
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Research Foundation of the State University of New York
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.)
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Publication of WO2011106526A2 publication Critical patent/WO2011106526A2/fr
Publication of WO2011106526A3 publication Critical patent/WO2011106526A3/fr
Priority to US13/594,288 priority Critical patent/US20130011492A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires

Definitions

  • the present invention relates generally to an electrochemical reduction method for deposition of a nanoparticle/chitosan composite layer and, in particular, a method for dispersion of metallic nanoparticles within a chitosan matrix on a metallic surface.
  • Metal nanoparticles act as catalysts in a variety of chemical processing methods, including conversion of organic compounds for use in energy generation such as polymer membranes for hydrogen fuel cells, chemical synthesis such as carbon-carbon bond formation, and oxidation reactions.
  • Fabrication of catalytic metal nanoparticles that include Silver (Ag), Gold (Au), Platinum (Pt) and Palladium (Pd) typically involve a three stage process that requires a metal salt in solution; a shaping or encapsulation agent, which is usually an organic molecule such as chitosan; and a strong reducing agent to reduce metal ions for the formation of nanoparticles.
  • a shaping or encapsulation agent which is usually an organic molecule such as chitosan
  • a strong reducing agent to reduce metal ions for the formation of nanoparticles For example, Huang, et al.
  • Chitosan is a linear polysaccharide of 2-amino-2-deoxy-D-glucopyranose obtained by deacetylation of chitin from crustaceans, mollusks, insects or fungi. Chitosan is the second most abundant natural biopolymer and there are broad ranges of applications for Chitosan. Chitosan, as well as chitosan loaded with antibiotic such as gentamicin, are biocompatible and have been applied to stainless steel bone screws to inhibit bacteria growth.
  • silane coupling agents are needed to create a bond between a chitosan film and titanium substrates used in dental implants. This requires a complex process involving several chemical treatments, including curing at elevated temperature, reaction with a cyano-oxysilane coupling agent and overnight exposure to a glutaraldehyde cross-linking agent. Such processes and agents are undesirable and often environmentally unsafe.
  • Huang requires pre-forming of the Au particles and stabilizing using citrate in a strong acidic solution prior to incorporation in chitosan, and also requires use of glutaraldehyde as a cross-linking agent.
  • Huang et al. Journal of Colloid and Interface Science 282 (2005), pages 26-31) describes a process, which requires use of sodium borohydride, which is a hazardous reducing agent, as does Adlim et al.
  • the disclosed method overcomes the above shortcomings by providing a method for electrochemically-induced deposition of a submersed stainless steel electrode in an acidic chitosan solution with a predetermined concentration of cationic silver by applying a potential to the stainless steel electrode for a predetermined amount of time, coating an oxy- anion rich passive layer of the stainless steel electrode with a first silver / nitro-chitosan layer, and continuing coating of the electrode to form a subsequent semi-crystalline silver / chitosan layer, and an apparatus developed from such method.
  • FIG. 1 illustrates electrochemical deposition on a cathode in accordance with the present invention
  • FIG. 2 is a Scanning Electron Microscope (SEM) image showing distribution of silver (Ag) nanoparticles within a chitosan coating adhered on stainless steel substrate utilizing the method of the present invention
  • FIG. 3 is a SEM image showing Ag nanoparticles formed near a surface of a chitosan layer deposited on stainless steel according to the method of the present invention
  • FIG. 4 is a profile view of a chitosan-based coating applied to stainless steel utilizing the method of the present invention
  • FIG. 5 charts data from X-ray Absorption Near Edge Spectroscopy (XANES) of X- ray absorption energy versus intensity of an Ag foil standard and of Ag nanoparticles formed in chitosan on stainless steel according to the method of the present invention;
  • XANES X-ray Absorption Near Edge Spectroscopy
  • FIG. 6 shows Synchrotron Fourier Transform Infrared (FTIR) spectra of a chitosan- Ag nanoparticle composite coating obtained from the method of the present invention and of a pure chitosan coating;
  • FTIR Synchrotron Fourier Transform Infrared
  • FIG. 7 provides comparative graphs of synchrotron Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy of an Ag nanoparticle containing chitosan coating to an Ag foil standard;
  • EXAFS Extended X-ray Absorption Fine Structure
  • FIG. 8 illustrates a process utilized to assess bonding strength of chitosan
  • FIG. 9 is a flowchart summarizing a method for electrochemically-induced deposition on an electrode according to the present invention.
  • the present invention provides a rapid technique utilizing room temperature solutions for electrochemical reduction to develop a nanoparticle/chitosan layer composite.
  • Electrochemical deposition allows for use of a reduced number of metal ions in the design and development of composites, with the entire process performed in an environmentally friendly manner.
  • an electrochemical method for polysaccharide attachment and film growth is provided via a negatively charged surface and an electron transfer process to generate the polysaccharide layer on a passivated stainless steel surface, similar to formation of biofilms by bacteria during biofouling. See U.S. Publication No. 2005/0154361 Al as a background regarding a chitosan-metal complex, the contents of which are incorporated herein by reference.
  • chitosan is electrophoretically deposited on stainless steel, primarily by applying a voltage to generate an elevated pH, preferably greater than 6.3, adjacent to the surface of cathode 101, as well as by electrostatic attraction of cationic chitosan from the solution to the cathode surface.
  • FIG. 1 illustrates coatings being deposited utilizing the room-temperature solution via electrostatic attraction. As shown in FIG. 1 , localized, near-surface changes in pH are created by polarization of the stainless steel substrate, i.e. cathode 101.
  • a strong surface adhesion occurs due to association of chitosan functional groups with chromate and other oxyanions in a passive layer 109 adjacent to the stainless steel substrate 101, with deposition performed under normal atmospheric conditions.
  • a chitosan film develops on the stainless steel substrate 101, with a pH gradient 107 elevating to above 6.3 as distance to the stainless steel substrate 101 decreases.
  • Applied voltage provides a rapid, simple way to form metallic nanoparticle structures in chitosan, which has applications in device fabrication and controlled surface biological and chemical effects.
  • Metallic nanoparticle spatial distribution in the chitosan coating i.e. a matrix of chitosan film formed on the surface of the electrode, is preferably controlled through the processing methodology, which allows for patterned deposition. Patterned deposition is obtained by application of pulsed voltage, thereby creating a layered structure.
  • the varied control of processing parameters, including pulsing of the deposition potential produces the layered structure containing silver (Ag) nanoparticles shown in FIG.
  • a passive film on stainless steel includes an inner layer of kinetic metal oxide barriers and oxyhydroxides, and an outer layer enriched in oxyanions. Since
  • polysaccharides including chitosan
  • chitosan are known to bind to chromate and other oxyanions in solution
  • an initial chitosan layer is created through electrostatic interaction with a cathodically charged stainless steel surface.
  • a type 304 stainless steel is utilized, the composition of which is known in the art.
  • an electrochemically-induced process is preferably used to deposit a chitosan/metallic nanoparticle coating on a stainless steel, functioning as an electrode.
  • a chitosan hydrochloric acid (HC1) solution having a pH of 4.5 to 5.0 was used.
  • a 300 series stainless steel was found to provide a preferred reactive surface for deposition due to a passive layer that allows strong film adhesion.
  • Deposition on type 304 stainless steel (18% Cr, 8% Nickel (Ni), bal. Iron (Fe)) at a cathodic potential was found to be rapid, with a thick layer of approximately 2-10 microns developing within five seconds to five minutes.
  • the coating method for electrochemically-induced deposition on an electrode submerses the electrode in an acidic chitosan solution with a predetermined concentration of cationic Ag.
  • a volume of 50 ml of a 0.001 to 0.1 M solution of silver nitrate (AgN0 3 ) was added to 50 ml of a solution containing 0.5 g of low molecular weight chitosan and 0.5 ml of 50% by volume acetic acid solution to provide a solution for electro-deposition.
  • a potential of -1.2 to -1.5 volts Ag/AgCl half cell potential was applied to the electrode.
  • Ag chitosan coating having an Ag nanoparticle size varying from 5 to 100 nm rapidly formed.
  • Cathodic polarization of a stainless steel surface in a mildly acidic chitosan solution results in formation of an adherent and functionally graded process.
  • Cationic chitosan is attracted to the cathodically-polarized surface where an initial, strongly bound layer is formed through complexation between amine (N3 ⁇ 4) groups and chromate oxyanions in an outermost layer of the passive film.
  • N3 ⁇ 4 groups amine (N3 ⁇ 4) groups and chromate oxyanions in an outermost layer of the passive film.
  • chitosan is deposited from solution due to the pH gradient near the stainless steel electrode surface. Trapped hydroxyl radicals generated by the cathodic process oxidize C-OH and amine groups to form carbonate-like and nitrate-like functionalities.
  • Ultra- Violet (UV) light exposure is preferably applied to dry the coating and further enhance the reactivity of hydroxyl radicals with chitosan, resulting in additional nitro groups.
  • the dried coating develops with additional beneficial mechanical and adhesive properties, and is believed to enhance crystallinity by multiple forms within a functionally-graded structure.
  • a dilute noble metal ion to the solution, such as from dissolution of an Ag salt, facilitates growth and retention of stable metal nanoparticles for biomedical, catalysis, sensor and other applications such as water filtration and nuclear test containment is possible.
  • the method of the present invention provides a durable coating with an improved mechanical durability for interfacing with other materials.
  • nanoparticle/chitosan composite provides an anti-biofouling coating.
  • FTIR Fourier Transform Infrared
  • Raman spectroscopy were used to provide chemical analysis of runctionalized polysaccharide nanostructured materials and coatings.
  • the Raman spectra from the electrochemically deposited coatings indicate a higher intensity in the primary amine bands, and occasionally in the phenolic region, as compared to stock powder.
  • X-ray Photoelectron Spectroscopy (XPS) was utilized as a surface sensitive technique to analyze C, N and O speciation and chemical environment to a depth of approximately 10 nm, to confirm surface chemistry.
  • FIG. 3 is an SEM image showing Ag nanoparticles formed in the chitosan coating deposited electrochemically on stainless steel
  • FIG. 4 is a profile view illustrating a structure obtained at the cathode by electrochemical deposition of a chitosan layer on the stainless steel electrode 101.
  • the electrode contains Cr, as in stainless steel 304, or Cr and Molybdenum (Mo), as in stainless steel 316.
  • Mo Molybdenum
  • an Ag/chitosan coating is deposited on a Cr 2 Mo bearing stainless steel surface 401 having an oxy-anion rich passive layer 403, including an Ag/nitro layer 405, a semi-crystalline Ag/chitosan layer 407, and a functionalized surface 409.
  • FIG. 5 is a graph of synchrotron X-ray absorption data comparing a silver foil standard 502 and silver nanoparticles 504 formed in chitosan on stainless steel, with the comparison indicating the metallic nature of the particles.
  • FIG. 6 provides results of Synchrotron FTIR spectroscopy performed on pure chitosan 602 and an electrochemically-formed layer with Ag nanoparticles 604, revealing several distinct differences, including the loss of a shoulder at wavenumbers 3440 (Al , A2) and replacement of the doublet at wavenumbers 1660/1590 by a single dominant peak at wavenumber 1600 (A3), both indicative of complexation at the amine group of chitosan. Additional changes occur in the peaks at wavenumbers 1300-1450 in the amide II region indicating additional complexation.
  • a further embodiment includes a tailored anti-microbial coating for cell scaffold applications.
  • a biological protocol was conducted by sterilizing Ag-chitosan coated substrates by immersing in 70% ethanol for two hours, after which the substrates were rinsed three times with sterile Phosphate Buffered Saline (PBS), and immediately transferred to a sterile tissue culture dish. The coatings were retained on the surface and appeared to be stable following treatment.
  • a cell suspension consisting of murine pre-osteoblasts (MC3T3-E1) was seeded onto the Ag-chitosan substrates at a density of 5,000 cells per square centimeter.
  • the cells were maintained in alpha Minimum Essential Medium (a-MEM) supplemented with 10% fetal bovine serum and 1% penicillin-streptomycin. After five days of incubation at 37°C (5% CO2, humidified), the samples were fixed with 3.7% formaldehyde and stained with 4',6-diamidino-2-phenylindole (DAPI) for nuclei visualization. Immunofluorescence micrographs were captured using a reflection microscope (Olympus 1X71) with a DAPI filter cube.
  • a-MEM alpha Minimum Essential Medium
  • DAPI 4',6-diamidino-2-phenylindole
  • Ag nanoparticles formed in the chitosan-based coating are stable for at least six months under general indoor atmospheric conditions of temperature and humidity, unlike Ag nanoparticles formed through simple wet chemical processes in chitosan. i.e. by use of chemical reductants, which reoxidize and agglomerate in less than 24 hours.
  • the Ag/ chitosan coating was also found to remain stable on a 304 stainless steel coupon following sterilization.
  • FIG. 8 To determine the chemical nature of the bonding layer created by the deposited matrix, stainless steel coupons 810 with deposited chitosan were immersed in liquid nitrogen for one minute. A razor was used to separate a large portion of the chitosan from the steel surface. Separated layers are shown in FIG. 8. Both the thin layer of deposited material, which remained strongly adhered to the surface 802 and the underside 804 of the removed layer, were observed to have undergone initial chemical analysis by Raman and X-ray Photoelectron Spectroscopy (XPS). FIG. 8 also provides spectra of the surface 802 and underside 804, which is found consistent not only with expected chitosan functional groups and bonding, but also consistent with formation of oxidized carbon and nitrogen species. A photoelectron spectra 805 obtained form underside 804 of the razor-removed coating, indicates formation of nitro and carbonyl groups.
  • XPS X-ray Photoelectron Spectroscopy
  • FIG. 9 is a flow chart summarizing the coating method for electrochemically- induced deposition on a stainless steel electrode of the present invention.
  • a stainless steel electrode is immersed in an acidic chitosan solution, preferably including 0.001 to 0.1 M AgNC>3.
  • the acidic chitosan solution is preferably 1 gram of low molecular weight chitosan in 100 mL of deionized water with an additional 0.5 mL of a 50% by volume acetic acid solution, which provides a pH of between 4.5 and 5.0.
  • a potential of -1.2 to -1.5 V versus the Ag/AgCl half cell potential is applied for a
  • the predetermined amount of time is preferably between five seconds and five minutes.
  • step 905 the stainless steel electrode is coated with an Ag/nitro-chitosan layer on an oxy-anion rich passive layer of the stainless steel electrode.
  • step 907 the coating continues to form a semi-crystalline Ag/chitosan layer.
  • the Ag nitro-chitosan layer and the semi-crystalline Ag/chitosan layer being 2-10 microns thick and including 5-100 nm Ag particles.
  • the stainless steel electrode is removed from the acidic chitosan solution and exposed to UV light for ten minutes at 365 nanometers wavelength, and 15,000 ⁇ /cm 2 at a distance of 10 cm.
  • samples are deposited on mechanically polished 304 and 316 stainless steel coupons.
  • the two metal substrates are used both to examine the role of substrate composition (Cr in 304 versus Cr and Mo in 316) on coating adhesion and interfacial chemistry.
  • Both the 304 and 316 coupon types are commonly used in biomedical and other applications.
  • the 304 stainless steel is a widely used austenitic stainless steel.
  • the 316 steel is a common Mo-bearing austenitic stainless steel. Both 304 and 316 type steel are used extensively in medical devices, instruments and implants for energy applications, including transport lines, fuel cell components, and support surfaces for catalysts, as well as to provide structural support in electronics and for water treatment applications.
  • the polished coupons were approximately one square centimeter in size, and were mechanically polished rather than electropolished, a process shown to sometimes alter surface chemistry. All samples were ultrasonically cleaned in propanol and doubly distilled water. Acetic acid-based chitosan solution was used for deposition as acetic acid is environmentally benign, easy to dispose of, and produces excellent coatings.
  • a PAR 600 potentiostat was used for electrochemical deposition, with voltage and time of deposition varied to optimize processing. Processing voltage was varied from -2.5 to -0.5 volts for a saturated Ag/AgCl electrode in 0.1 V increments. Processing time was varied from five seconds to two minutes. Electrode/sample geometry during deposition was standardized through use of a custom test stand to hold the surface, i.e. the working electrode, at a set distance from the reference electrode, i.e. the Ag AgCl half-cell and the Pt counter electrode.
  • Electrochemical solutions were varied in terms of concentration: concentration of chitosan/acetic acid varies for pure chitosan coating deposition, and concentration of chitosan/acetic acid and AgNC»3 varies for Ag-containing deposition. All deposition was conducted in open, i.e. aerated, solution.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

L'invention concerne un procédé de revêtement d'une électrode en acier inoxydable par dépôt induit par électrochimie par submersion de l'électrode en acier inoxydable dans une solution acide de chitosane incluant de l'argent cationique, application d'un potentiel à l'électrode en acier inoxydable pendant une période de temps prédéterminée, revêtement d'une couche passive riche en oxy-anion sur l'électrode en acier inoxydable avec une première couche de nanoparticules d'argent/nitro-chitosane, et poursuite du revêtement de l'électrode pour former une autre couche semi-cristalline de nanoparticules d'argent/chitosane.
PCT/US2011/026075 2010-02-24 2011-02-24 Procédé de formation électrochimique de nanoparticules nobles dans une matrice de chitosane Ceased WO2011106526A2 (fr)

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US13/594,288 US20130011492A1 (en) 2011-02-24 2012-08-24 Electrochemical deposition of noble metal and chitosan coating

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US30764810P 2010-02-24 2010-02-24
US61/307,648 2010-02-24

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013116618A1 (fr) * 2012-02-03 2013-08-08 The Research Foundation Of State University Of New York Synthèse électrochimique de nitro-chitosane
WO2013116619A1 (fr) * 2012-02-03 2013-08-08 The Research Foundation Of State University Of New York Synthèse électrochimique de chloro-chitosane
WO2013119889A1 (fr) * 2012-02-09 2013-08-15 The Research Foundation Of State University Of New York Synthèse de nanoparticules de palladium
ITMI20131468A1 (it) * 2013-09-06 2015-03-07 Nextmaterials S R L Processo per la realizzazione di film self standing a base di macromolecole di origine naturale o sintetica caratterizzati da micro-pattern a porosità controllata
CN117626365A (zh) * 2023-12-08 2024-03-01 广东盈华电子科技有限公司 一种用于载体超薄铜箔的复合剥离层及其应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8005526B2 (en) * 2005-08-31 2011-08-23 The Regents Of The University Of Michigan Biologically integrated electrode devices
WO2009120151A1 (fr) * 2008-03-28 2009-10-01 Nanyang Technological University Membrane faite à partir d'un matériau nanostructuré
US20090297581A1 (en) * 2008-05-28 2009-12-03 Boston Scientific Scimed, Inc. Medical devices having electrodeposited coatings

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013116618A1 (fr) * 2012-02-03 2013-08-08 The Research Foundation Of State University Of New York Synthèse électrochimique de nitro-chitosane
WO2013116619A1 (fr) * 2012-02-03 2013-08-08 The Research Foundation Of State University Of New York Synthèse électrochimique de chloro-chitosane
CN104105712A (zh) * 2012-02-03 2014-10-15 纽约州立大学研究基金会 氯代壳聚糖的电化学合成
US9518077B2 (en) 2012-02-03 2016-12-13 The Research Foundation For The State University Of New York Electrochemical synthesis of chloro-chitosan
WO2013119889A1 (fr) * 2012-02-09 2013-08-15 The Research Foundation Of State University Of New York Synthèse de nanoparticules de palladium
US9932685B2 (en) 2012-02-09 2018-04-03 The Research Foundation For The State University Of New York Synthesis of palladium nanoparticles
ITMI20131468A1 (it) * 2013-09-06 2015-03-07 Nextmaterials S R L Processo per la realizzazione di film self standing a base di macromolecole di origine naturale o sintetica caratterizzati da micro-pattern a porosità controllata
EP2845612A1 (fr) * 2013-09-06 2015-03-11 NextMaterials S.r.l. Procédé de fabrication de films auto-portés faits de polymères naturels ou synthétiques présentant un micro-motif poreux.
CN117626365A (zh) * 2023-12-08 2024-03-01 广东盈华电子科技有限公司 一种用于载体超薄铜箔的复合剥离层及其应用

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