Nanophase Manganese Oxides Coated Nonwoven Applications

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Nanophase Manganese Oxides Coated Nonwoven
Applications

• Rajan K. Vempati, Ph. D.
• ChK Group, Inc., Plano, TX
• Gajanan Bhat, Ph. D.
• University of Tennessee, Knoxville, TN
• Richard W. Wagner, Ph. D.
• Phycotransgenics, LLC, Indianapolis, IN

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Presentation Outline

• Various Mn Oxidation and Stabilization by
  phenylenediamines (PDA)
  Isomers
• Morphology and Particle Size
• Mn Oxidation States Confirmation
• Visible Spectroscopy and Cyclic Voltammetry
• Sensors
• Comparison of KMnO4 and Mn(VII) Oxide Reaction
  Mechanisms
• Mn-Oxide Coating on Solid Support
• Mn(VII) Oxide Advantages
• CWAs Surrogates Studies
• Mn(VII) Oxide Coating on Fabrics
• Odor Control
• Metal Polish
• Algaecide and Biocide
• Military and Civilian Applications

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Nanophase Mn OxidesDr. Rajan K. Vempati and Dr.
David L. Son(US Patent No 6,953,763)

• First to report stabilization of various Mn
  oxidation in solid forms, i.e., Mn(II), Mn(III)
  and Mn(VII) using phenylenediamines (PDA) isomers
• In natural environment Mn(III)- and
  Mn(VII)-oxides are unstable and
  dis-proportionates to Mn(II)- and/or Mn(IV)
  -oxides
• Color distinct
• Mn(II) Oxide - pink
• Mn(III) Oxide - green
• Mn(IV) Oxide - brown to black
• Mn(VII) Oxide - violet

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PDA Applications

• Kevlar Protective Garments
• Bullet proof vest
• Fire protection
• Hair Dyes

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Various Mn Oxidation States Stabilized by
Phenylenediamine Isomers
a). Mn(II) Oxide Stabilized by O-PDA b).
Mn(III) Oxide Stabilized by p-PDA
dihydrochloride c). Mn(IV) No PDA isomer
stabilized this oxidation state d). Mn(VII)
Stabilized by p-PDA e). Mixed Mn(III)- and
Mn(VII) oxides Stabilized by p-PDA in the pH
range of 5 to 6.5. The color of the minerals
is bluish green. No reaction with m-PDA
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Nanophase Mn(VII) Oxide SEM Image

Scale Bar 200 nm
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Fate of 1,4-PDA A NMR Study
Fig. (a) Before reaction, (b) and (c) loss of
1,4-PDA after synthesis of ZSM-5-supported
Mn(VII).
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Mn Oxidation StatesandChemical Sensors
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Confirmation of Various Mn Oxidation States by
Cyclic Voltammetric Technique
Dr. Mark Schell and Dr. E. Swamy Southern
Methodist University

• Mn(II) voltammetic feature similar to Mn(II)
  salt. When potential applied towards positive
  direction, Mn(III) and Mn(IV) peaks were observed
  and in reverse direction Mn(III) and Mn(II) peaks
  observed.
• Mn(III) voltammetric feature - oxidized to Mn(IV)
  when potential was applied towards positive
  direction and in reverse direction reduced to
  Mn(III).
• Mn(VII) voltammetric feature similar to KMnO4
  under same conditions. No peaks in positive
  direction and two reduction peaks, Mn(III) and
  Mn(II) in reverse direction.

• Solid line Mn(II)
• Dotted line Mn(III) and
• Dashed line Mn(VII)

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Visible Spectra of Various Mn-Oxidation States
Advantage Optical Sensor to detect exhaustion
of the starting material
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Color Change

• Mn(VII) Oxide (Violet Color)
• Mn(IV) Oxide (Brown/Black Color)

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Mn-Oxide Coating to Ion Exchangers
Mn(VII) Oxide Particles Clay
Particle Clay-Coated Mn(VII) Oxides
Particles

• Advantages
• Prevent nanoparticles dispersion in air
• Increases the reactive surfaces, important as the
  reaction occurs on the surfaces
• Chemical Bonds (dont fall apart)
• Decreases chemical costs (5 to 10)

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Mn(VII) Oxide Advantages (I)
1. Environmentally friendly. 2. Rapid
Manufacturing. 3. Site-specific manufacturing or
safe transportation in powder, slurry or aerosol
form. 4. Easy to handle with no specialized
equipment and with minimum supervision. 5. The
Mn(VII) mineral (violet color) changes to brown
color indicating its consumption during the
reaction.
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Mn(VII) Oxide Advantages (II)
6. Long shelf life, the material is stable and
dispersed . 7. Operates in polar and non-polar
solvents. Surface mediated reaction, and 8.
No hazardous byproducts anticipated therefore,
the spent dust or dried material may be either
vacuumed or wiped with moist cloth, and
treated with 70C water before disposal.
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Reaction Chemistry Between Nanophase Mn(VII)
Oxide and KMnO4 Compound

• Mn-Compound Reactant
  Product Reactions
• KMnO4 Cyclohexylamine
  Cyclohexanone Azo-Dye
• Mn(VII) Oxide Cyclohexylamine
  Gaseous Byproducts Lewis Acid
• KMnO4 Cyclohexanone
  Cyclohexanone -
• Mn(VII) Oxide Cyclohexanone
  Gaseous Byproducts Lewis Acid

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Mn(VII)-Oxide a Strong Lewis Acid(Superacid)

• Lewis Acids Accept lone pairs of electrons
• e.g., N, S, O and P
• Lewis Bases Donate lone pairs of electrons

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CWAs Surrogate StudiesUS Patent Pending
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Experiment Setup

• 5000 ppm of surrogates in 20 mL dichloromethane
• 2-chloroethyl ethyl sulfides (CEES)
• dimethyl methylphosphonate (DMMP)
• 1 g of the 10 Mn-Coated Clay or 2 g KMnO4
• 70ºC for 3 hrs
• 100 mg of the surrogate / g of clay coated
• Mn(VII) oxide destroyed compared to 0.15
  to 22 mg/g sorbed by other solid Decon agents.

• Temperature, Kinetics and Stoichiometric Studies
  Ongoing

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a) Starting material containing 5,000 ppm
of 2-chloroethyl ethyl sulfide (2-CEES)
b) Two gm of KMnO4 reacted with 5,000 ppm of
2-CEES
Counts
c) One gm of clay coated with 10 Mn(VII)
oxide reacted with 5,000 ppm of 2-CEES.
Pure Clay No CEES Destruction
Minutes
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a) Starting material containing 5,000 ppm of
dimethyl methyl phosphonate (DMMP),
Counts
b) Two gm of KMnO4 reacted with 5,000 ppm
of DMMP
c) One gm of clay coated with 10 Mn(VII)
oxide reacted with 5,000 ppm of DMMP
Minutes
Pure Clay No DMMP Destruction.
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Fabrics Incorporated NM7O
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Three different nonwoven fabric samples coat on
to the MN7O-clay

• A-80gsm needle-punched cotton nonwoven supplied
  by the Cotton Incorporated, Raleigh, NC
• Cotton Needled.
• A through air bonded cotton/PLA web produced at
  the University of Tennessee, Knoxville, TN (UTK)
  
• CottonPLA Bico (Single and Double dip)
• The meltblown polyurethane web produced at
  TANDEC by Dr. Wadsworth
• PU

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Incorporation of Mn7O

• Solution Mn (II) and Mn (III) in water.
• Cotton/PLA Nonwoven
• Nip Pressure 3 bar
• Drying Temperature 150ºC
• Line Speed - 0.2 m/min (4min res. Time)

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MATHIS Laboratory padder/coater

• Features
• Fabrics can be padded/coated/ laminated and
  cured
• Fabric width app. 30 cm

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Schematic of padding and curing process
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UnCoated- and Coated-Fabrics Properties
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Cotton PLA BiCO Before and After NM7O Coating

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1 Cotton Needle, 2 CottonPLA Bico Single
Dip 3 CottonPLA Bico Double Dip, 4 PU
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1 Cotton Needle, 2 CottonPLA Bico Single
Dip 3 CottonPLA Bico Double Dip, 4 PU
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1 Cotton Needle, 2 CottonPLA Bico Single
Dip 3 CottonPLA Bico Double Dip, 4 PU
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Odor Removal

• S-based
• Sulfides and Mercaptans
• N-Based
• Amides

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Mercaptan Study

• Took a known quantity of Mn-coated fabric in a
  test tube
• Added 800 ppm of 2-merpatoethanol (diluted in 10
  mL CDCl3 (non-polar solvent)
• Capped and agitated gently for a known amount of
  time
• Smell test
• GC MS
• NMR

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Removal of Mercaptan Odor using Supported
Nanophase Mn(VII) Oxide (NM7O) Coated Clay
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Di-sulfides Applications

• Fruity or Pleasant Smell
• Odorless garlic
• Perfume industry
• Petrochemical Catalysts

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Silverware Polish

• The double dip NM7O-clay incorporated cotton
  fabric was utilized to polish silver.
• The violet colored fabric changed to brown during
  silverware polish, indicating that it oxidized
  organic S compounds which are primarily
  responsible for silverware tarnishing.

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The Nanophase Mn(VII) Oxide (NM7O) Coated Non
Woven Fabric being Used to Polish the Tarnished
Silver Bowl
NM7O Coated Non Woven Fabric
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Silver Bowl After Treatment with NM7O Coated
Non-Woven Fabrics
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Algaecidal and Biocidal Properties
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Biocide Study

• The LB media were inoculated with a single
  colony of E. Coli and allowed to grow for 14 hrs
  at 37C.
• Three tubes were treated with 300µl of the NM7O
  and returned to for another 14 hrs with a
  control.
• The tubes are then plated on LB agar with 100µl
  of sample from the tubes. The Petri plates have
  Para film placed around the edges and the plates
  are returned to the incubator overnight.
• Interestingly, the violet colored NM7O changed to
  brown color during the destruction of E. Coli.

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E.coli Control Plate
E.coli lawn
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10 NM7O Streak Plate
E.Coli colony

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Destruction Rate

• Control contained 1 x 10E8 cells.
• If all cells survived - 1 x 10 E6 cells to grow
  on the plate (100 ml sample).
• Only 4 cells grew the survival rate was 4/1
  x 10E6 or 0.0004.

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Algae Study

• Fabrics cut into approximately 0.025 sq. in. and
  inoculated with 200µl of (3 x 10E6 cells/ml) of
  a three day culture of Chlamydomonas reinhardtii
  (green algae).
• The samples were kept in separate Petri dishes
  and Para filmed. The dishes were kept at 20-25ºC
  for 24 hrs.
• The individual samples were then placed into
  125ml Erlenmeyer flask containing 50 mls of TAP
  media and on a platform shaker for three days in
  full light and at 20-25ºC with the shaker set at
  130 rpm.

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Algal Treatment Study
Control Cotton
Washed Cotton with Mn(VII)
Unwashed Cotton with Mn(VII)
Cotton with Mn(III)
Polyurethane with Mn(VII)
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Military and Civilian Applications

• .
• Odor control, e.g., S- and N-bearing compounds
• Industrial workers
• Sports wear
• Undergarments
• Hospital Beds
• Diapers
• 2. Incorporate Mn(VII) mineral in soldiers
  clothing for protection
• against CWAs so, as to provide greater
  flexibility/
• movement for the army to operate during
  terrorist attack.
• Environmentally friendly Metal Polish,
• Medical gauzes, and
• 5. Develop Mat technology for treating TICs
  spills, which can be
• utilized by Haz-Mat and Spill response team.

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Technology Development Team
First Responders and Haz-Mat Team
Contractors
Small Businesses
ChK Group, Inc.
Big Businesses
Private Laboratories
Federal Laboratories
Universities

• Government Grants
• Private Grants
• Licensing Fees