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Microporous and Mesoporous Materials 108 (2008) 77–85

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Hydrophilic and antimicrobial low-silica-zeolite LTA and

high-silica-zeolite MFI hybrid coatings on aluminum alloys
Derek E. Beving, Cory R. O’Neill, Yushan Yan *

Department of Chemical and Environmental Engineering, University of California, Riverside, CA 92521, USA

Received 21 December 2006; received in revised form 14 March 2007; accepted 17 March 2007
Available online 28 March 2007

Abstract

A hydrophilic and antimicrobial two-layer zeolite composite coating was formed on aluminum alloys. The base layer is a high-silica-
zeolite (HSZ) MFI coating formed directly on the aluminum alloy by in situ crystallization. The top layer is a crystalline zeolite hybrid
coating of low-silica-zeolite (LSZ) LTA (zeolite A, or ZA) crystals imbedded within a HSZ-MFI matrix and is formed by a seeded
growth method. The two-layer composite coatings are demonstrated by using ASTM D 3359B-02 method to have excellent adhesion
to the aluminum alloy substrates. The hybrid layer is hydrophilic with contact angles below 5 and when they are silver-ion exchanged
the hybrid coating is highly antimicrobial.
 2007 Elsevier Inc. All rights reserved.

Keywords: Zeolite; Coating; Hybrid; Composite; Hydrophilic; Antimicrobial

1. Introduction that no preformed zeolite crystals are used in the synthesis.

Polycrystalline zeolite membranes, films, and coatings
have been demonstrated to be useful in membrane separa-
tions, membrane reactors, sensors, adsorption, catalysis,
low-k dielectrics, corrosion-resistant coatings, hydrophilic
coatings, antimicrobial coatings, heat pumps, and thermo-
electrics [1]. These zeolite membranes, films, and coatings
are normally synthesized hydrothermally in a sealed reac-
tor under autogenous pressure. The synthesis techniques
can be broadly classified into two types, in situ crystalliza-
tion and seeded (or secondary) growth. In situ crystalliza-
tion is a one-step film deposition process where the
substrate to be coated is directly submerged in the synthesis
solution and the zeolite crystals are formed ‘‘in situ’’ (or
directly) on the substrate surface, followed by their growth
to form a continuous zeolite layer over the substrate [2].
The term ‘‘in situ crystallization’’ originates from the fact
*
Corresponding author. Tel.: +1 951 827 2068; fax: +1 951-827-5696.
E-mail address: yushan.yan@ucr.edu (Y. Yan).
Seeded growth is a film deposition process where a layer of
preformed zeolite crystals is deposited on the substrate
prior to the subsequent hydrothermal treatment. The pre-
deposition of a zeolite seed layer can effectively decouple
zeolite nucleation from zeolite growth [3]. There are a
few variations on these two methods that are not discussed
here.
The hydrophilicity and hydrophobicity of zeolite mem-
branes, films, and coatings is dependent upon the silicon-
to-aluminum ratio of the zeolite making up the coating.
As used herein, pure-silica zeolites have a silicon:aluminum
ratio of infinity, high-silica zeolites (HSZ) have a sili-
con:aluminum ratio greater than 50, intermediate-silica zeo-
lites have a silicon:aluminum ratio between 50 and 2, and
low-silica zeolites (LSZ) have a silicon:aluminum ratio less
than 2. Pure or high-silica zeolites are hydrophobic, or
not significantly hydrophilic, whereas, their intermediate-
silica and low-silica counterparts are hydrophilic. The
synthesis solutions for many of the pure-silica-zeolite (e.g.,
silicalite, or PSZ-MFI) and high-silica-zeolite (e.g., ZSM-5,
or HSZ-MFI) types of zeolite coatings are characterized

1387-1811/$ - see front matter  2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2007.03.029
78 D.E. Beving et al. / Microporous and Mesoporous Materials 108 (2008) 77–85
by pHs that are mildly alkaline or neutral. By contrast, low-
silica-zeolite coatings such as faujasite (zeolite X and zeolite
Y) and zeolite A are characterized by extremely alkaline syn-
thesis solutions.
The high alkalinity of the low-silica-zeolite synthesis
solutions has restricted the types of metal substrates used
to support low-silica-zeolite coatings to those that are more
resistant to oxidation like stainless steels. Current zeolite
coatings synthesized directly on aluminum and its alloys
by both in situ crystallization and seeded growth include
pure-silica and high-silica-zeolite coatings. When alumi-
num substrates are immersed in low-silica-zeolite synthesis
solutions with its characteristic high pH, the aluminum
begins to oxidize and may possibly totally corrode before
a zeolite coating can form thereon.
Low-silica-zeolite, hydrophilic coatings have been suc-
cessfully synthesized by in situ crystallization on stainless
steel and have shown great utility [4–6]. Munoz et al. dem-
onstrated that hydrophilic zeolite coatings on stainless steel
can increase the heat transfer rate and efficiency for heat
exchanger applications [5]. The heat transfer rate and effi-
ciency were increased through a decrease in evaporation
time and an increase in the wetting limit temperature of
water droplets on the surface of hydrophilic zeolite coat-
ings [5]. McDonnell et al. and O’Neill et al. showed that
low-silica-zeolite coatings on stainless steel are hydrophilic
and antimicrobial and are useful in condensers for water
separation in space [4,6]. The antimicrobial capability
was achieved by silver-ion exchange into the zeolite coat-
ings [4,6]. The low-silica-zeolite coatings remained hydro-
philic and exhibited no loss in antimicrobial activity after
submersion in water for 8 weeks [6].
For the heat transfer applications mentioned above, it is
highly desirable to replace stainless steel with aluminum
and aluminum alloys. Aluminum’s thermal conductivity
is approximately 15 times that of stainless steel and this
can translate into a smaller size for a heat exchanger [7].
And this is why high conductivity metals such as aluminum
and aluminum alloys are preferred as heat exchanger parts
(e.g., hot coils and chilled coils and fins) in an air condi-
tioning system. In addition, aluminum and aluminum
alloys are light in weight and mechanically strong [7]. Thus
if the low weight and high thermal conductivity of alumi-
num and aluminum alloys can be combined with the
hydrophilic and antimicrobial ability of low-silica-zeolite
coatings, an excellent technology would be available for
applications in weight and size conscious environments.
Unfortunately, to date, there has been no successful for-
mation of a low-silica-zeolite coating directly on aluminum
substrates. Yan and Beving have recently demonstrated a
three-step method to combine for the first time low-silica-
zeolite coatings with aluminum alloy substrates [8]. This
consisted of a stack of three zeolite coating layers with the
top most layers a low-silica-zeolite coating of a single crys-
talline zeolite species, zeolite Y (ZY). A corrosion-resistant
high-silica coating served as the base layer and protected the
aluminum alloy from oxidation during the low-silica-zeolite
synthesis. The middle layer was a hybrid coating made up of
low-silica-zeolite ZY seed crystals embedded within a high-
silica-zeolite MFI matrix and it functioned as an adhesive
bridge between the high-silica-zeolite base layer and the
low-silica-zeolite top layer. Even though the low-silica-zeo-
lite coating is not formed directly on the aluminum sub-
strate, Yan and Beving effectively coupled the low-silica-
zeolite properties with the advantages of aluminum as a
substrate [8]. However, the generation of this three-layer
stacked coating requires three separate hydrothermal syn-
theses, one in situ crystallization and two seeded growth,
which can become time and labor intensive. Because the
stacked coating consists of three layers of different zeolites
with different synthesis methods, adhesion between the lay-
ers is of concern. Also, the three-layer stack coating may not
be useful for applications requiring very thin hydrophilic
coatings, because each coating layer would innately have
a minimum thickness that when combined, may exceed
the required application thickness.
In this study, we demonstrate the formation of a two-
layer hydrophilic and antimicrobial hybrid zeolite coating
of tunable thickness on aluminum alloys with excellent
adhesion. The hybrid coating is a mixed zeolite composite
coating made from low-silica-zeolite (zeolite A) seed crys-
tals imbedded in a matrix of high-silica-zeolite MFI, simi-
lar to the middle layer in the three-layer stack of Yan and
Beving [8]. We show for the first time a purely crystalline,
mixed zeolite hybrid coating made from disparate zeolite
species as a functional end product. This zeolite hybrid
coating has great utility and its function and application
can be easily tuned by changing the zeolite species used
to generate it.
2. Experimental
2.1. Coating solution formulation
HSZ-MFI coatings were prepared by in situ hydrother-
mal crystallization method. First, a clear synthesis solution
with molar composition 0.16TPAOH:0.64NaOH:TEOS:
92H2O:0.0018Al (gram composition 17.03 g TPAOH,
5.36 g NaOH, 43.60 g TEOS, 336.00 g H2O, 0.0105 g Al)
was prepared by dissolving aluminum powder (200 mesh,
99.95+ wt%, Aldrich) in sodium hydroxide (99.99 wt%,
Aldrich) and double de-ionized H2O (ddH2O) followed
by drop-wise addition of tetrapropylammonium hydroxide
(TPAOH, 40 wt%, aqueous solution, SACHEM) and tetra-
ethylorthosilicate (TEOS, 98 wt%, Aldrich) under stirring.
The clear solution was aged at room temperature for about
4 h under stirring before use.
Zeolite A seed crystals were prepared according to
Smaihi et al. [9], with slight modifications. A sodium
silicate solution with molar composition of 1.0SiO2:7.5-
NaOH:102H2O was prepared by dissolving 5.55 g sodium
silicate, Na2Si3O7 (27% SiO2, 17% NaOH, Aldrich) and
6.73 g NaOH in 72.75 g double di-ionized H2O (ddH2O).
A sodium aluminate solution with a molar composition
 D.E. Beving et al. / Microporous and Mesoporous Materials 108 (2008) 77–85
of 1.0Al2O3:15NaOH:197H2O was prepared by dissolving
2.73 g sodium aluminate (Na2O Æ Al2O3 Æ 3H2O, Spectrum)
and 6.5 g NaOH in 43.65 g ddH2O. The solutions were stir-
red at room temperature until complete dissolution of sol-
ids. The sodium silicate and sodium aluminate solutions
were mixed together and vigorously stirred for 30 min.
The mixed solution was placed in a 40 C convection oven
for 17 h. The solid phase was recovered after 5–6 cycles of
centrifugation (5000 rpm for 10 min), decanting and redi-
spersion in de-ionized H2O (DI H2O) by vortexing and
sonication. After the final centrifugation and decantation
the solids were resuspended in 100% ethanol.
2.2. Substrate pretreatment
Aluminum alloys (AAs) were commercially purchased.
AA-7075-T6 and 5052-H32 were purchased from American
Aerospace Materials, Monterey Park, CA. AA-2024-T3
and AA-6061-T4 were purchased from Advanced Alloys,
Inc. Rancho Cucamonga, CA. The substrates were sized
to 2 cm · 3.5 cm coupons and cleaned at 60 C for 1 h in
an Alconox detergent solution prepared with 3.0 g Alco-
nox in 400 mL DI H2O. The substrates were then rinsed
under DI H2O with mild rubbing. Substrates were dried
with compressed air and kept at ambient conditions for less
than 1 h before immersion in HSZ-MFI synthesis solution.
2.3. HSZ-MFI coating deposition
A 45 mL Teflon-lined Parr autoclave was used as the
synthesis vessel and the substrate was fixed vertically inside
the synthesis solution using a Teflon holder. Crystalliza-
tion was carried out in a convection oven at 175 C for
16 h. The autoclave was then removed and quenched with
tap water. The coated sample was rinsed with DI H2O and
dried in ambient room air for at least 12 h before character-
ization and coating with zeolite A seed crystals. This coat-
ing is referred to as the MFI coating or layer and the MFI
coating on the aluminum alloy is designated from the top
down as MFI/AA.
2.4. Zeolite A seeded layer
Zeolite A (ZA) seed crystals were resuspended in 100%
ethanol to a concentration of 1 g ZA seed crystals in
5 mL ethanol. The MFI coated aluminum alloy substrates
(MFI/AA) were submersed in the ZA seed solution for
2 min, removed and air-dried for at least 4 h prior to char-
acterization and the subsequent HSZ-MFI short synthesis.
2.5. HSZ-MFI short synthesis
To securely anchor the ZA seed crystals to the underly-
ing MFI base layer the ZA seeded base layer is subjected to
a quick synthesis in HSZ-MFI solution. The same synthesis
solution and methods as the MFI base layer were used. The
variation is that the synthesis time is shortened to 4.5 h.
79
This results in a crystalline hybrid zeolite coating or layer
composed of ZA seeds within an MFI matrix and this layer
is referred to as the hybrid coating or layer. The complete
coating stack on the aluminum alloy is designated as
hybrid/MFI/AA and the collective coating is a composite
coating of LSZ and HSZ.
2.6. Silver ion exchange
The antimicrobial properties of the LSZ–HSZ compos-
ite coatings are conferred by silver ions exchanged with
sodium ions within the pores of the zeolite hybrid coating.
The silver ion-exchange was performed by inserting a
corner of the coated substrate in a slit within a hollow
polypropylene ball and floating them in a gently stirred
0.01 M solution of AgNO3 in an amber colored polypro-
pylene bottle at room temperature for 6 h.
The coupons were washed thoroughly under DI water
and then soaked in DI water for 1 h. Semiquantitative ele-
mental analysis of the hybrid coating by energy dispersive
X-ray spectroscopy (EDS) was used to confirm the com-
plete exchange of sodium with silver.
3. Characterization
3.1. XRD, SEM, and EDS
The X-ray diffraction (XRD) patterns were obtained on
Siemens D-500 diffractometer using Cu Ka radiation.
MFI/AA, ZA seeded MFI/AA, hybrid/MFI/AA samples
and ZA seed crystals were directly used for XRD analysis
and were fixed and aligned in the sample holder carefully
to minimize shifts in 2h angles. Scanning electron micro-
scope (SEM) micrographs were obtained on a Philips
XL30-FEG scanning electron microscope operated
between 5 and 20 kV. An Au/Pd coating was applied to
MFI/AA samples by sputtering for 30 s for both surface
and cross-sectional SEM imaging. MFI/AA samples were
etched for cross-sectional SEM imaging by dipping the
MFI/AA samples in 49 wt% HF for 5 s. Hybrid coated
MFI/AA samples were etched for cross-sectional analysis
in 1 wt% HF for 1 s. The silicon to aluminum ratio of the
different zeolite layers and confirmation of the complete
exchange of sodium with silver was determined by semi-
quantitative energy dispersive X-ray spectroscopy (EDS),
performed on a Philips XL-30 scanning electron micro-
scope equipped with an EDAX EDS analytical system.
3.2. Adhesion
Adhesion of the LSZ–HSZ composite coatings to the
AA substrates was measured according to American Soci-
ety for Testing and Materials (ASTM) ASTM D 3359B-02
[10]. The adhesion test kit was purchased from Paul N.
Gardner Company, Inc. The cutting tool was fitted with
a blade containing 11 teeth spaced 1.0 mm apart. Coated
substrates were secured to the lab bench by a C-clamp
80 D.E. Beving et al. / Microporous and Mesoporous Materials 108 (2008) 77–85
and the cutting tool was used to make the cross-cut pattern
at 90 angles through the coating. The coating was brushed
lightly with a soft brush after each cut to remove excess
debris from the surface. Permacel 99 tape was applied to
the cut surface and rubbed with the eraser end of a pencil
to ensure good contact with the coating and then removed
after 90 s. Samples were evaluated under a lighted magnify-
ing glass (7· magnification) and rated according to the
ASTM rating scheme.
3.3. Contact angle measurement
The water contact angles of all the different coatings
were measured using a VCA Optima XE (AST Products,
Inc.). Coated substrates were placed onto the sample stage
and a 28 gauge blunt-tip needle was attached to a VCA
Optima XE mechanically controlled micrometer for dis-
pensing a 2 lL ddH2O droplet onto the surface of the
zeolite coated surface of the coupons. Contact angle mea-
surements were determined by using the VCA Optima
AutoFAST contact angle calculation software. Ten mea-
surements were made on each sample coupon and three
samples of each type were analyzed.
3.4. Antimicrobial testing
The antimicrobial function was tested according to pub-
lished protocols [4,6,11]. Individual colonies of Escherichia
coli (JM 109) grown on Luria–Bertani (LB) plates were
transferred with sterile toothpicks to sterile test tubes con-
taining LB broth and incubated at 37 C overnight with
shaking. The resultant cultures were centrifuged at
3000 rpm at 4 C for 15 min and resuspended in Butter-
fields Buffer (BFB) to an optical density at 540 nm between
0.1 and 1.0.
BFB (6.5 mL) was added to sterile 60 mm · 15 mm Petri
dishes containing sterile Teflon rings. The silver-
exchanged and non-exchanged hybrid/MFI/AA coupons
were exposed to ultraviolet light for 20 min to ensure steril-
ity prior to biocidal testing. The sterile sample coupons
were placed onto the Teflon rings and 0.5 mL of the
E. coli suspension containing greater than 1 · 106 colony-
forming units (CFU) was placed on the coupon and incu-
bated at 37 C at a constant relative humidity of 60% for
0, 4, and 24 h. Six samples each of the silver-exchanged
and non-exchanged hybrid/MFI/AA coupons were used
for each incubation period. After incubation, the Teflon
rings were removed and the incubated coupons immersed
in the BFB at the bottom of the Petri dishes. Each coupon
was scraped with a sterile cell spreader three times along
the major axis and three times along the minor axis. The
cell spreader and coupon were rinsed with 3 mL BFB,
bringing the total BFB volume within the Petri dish to
10 mL. The rinsed coupons were removed and the buffer
solution was serially diluted to an appropriate dilution
for enumeration of CFUs by bacterial plating. 100 lL ali-
quots of the diluted solutions were spread on LB agar
plates and incubated at 37 C for 24 h. The CFUs were
counted visually and back-calculated to determine the
number of CFUs surviving on the coupons after each incu-
bation time.
4. Results and discussion
The LSZ–HSZ composite coating is a two-layer coating
generated by two hydrothermal syntheses. The base layer is
a high-silica-zeolite MFI coating synthesized by in situ
crystallization directly on the aluminum alloy (AA) and
is designated MFI/AA. The HSZ-MFI coating is needed
for applications requiring corrosion resistance to prevent
the aluminum alloy from corroding. Pure silica and
high-silica-zeolite coatings have been shown to protect alu-
minum alloys from corrosion in alkaline, acidic and aggres-
sive pitting corrosive media [12–14]. Fig. 1a and b shows
SEM images of the HSZ-MFI surface and thickness
(approximately 5 lm), respectively. The MFI/AA is then
coated with ZA seed crystals by dipping the HSZ-MFI/
AA samples in a ZA seed crystal suspension in ethanol
and is now designated as ZA seed/MFI/AA. Fig. 1c shows
the ZA crystal seed layer on top of the MFI layer and the
inset shows that the ZA crystals have a size range between
200 and 500 nm. The ZA seeded MFI/AA samples are then
submersed in the HSZ-MFI synthesis solution and are sub-
jected to a brief hydrothermal synthesis for 4.5 h.
This brief hydrothermal synthesis results in a hybrid
zeolite layer made up of ZA crystals and a HSZ-MFI crys-
talline matrix surrounding the zeolite A crystals. The com-
pleted two-layer coating is referred to as a composite
coating; the top zeolite layer is a hybrid layer or coating
and the base layer is a HSZ-MFI coating. Fig. 1d shows
the surface of the hybrid layer and the inset is a higher
magnification of the surface. The thickness of the hybrid
zeolite layer is about 4.5 lm (Fig. 1f). Fig. 1e and f shows
the MFI base layer and the hybrid zeolite top layer.
The thicknesses of the HSZ-MFI coating and of the
hybrid zeolite coating are both adjustable. The HSZ-MFI
coating is generated by in situ crystallization and by vary-
ing the hydrothermal synthesis time we can tune its thick-
ness. Shorter synthesis times result in thinner coatings
and longer periods of synthesis will generally generate
thicker coatings. The function of the HSZ-MFI coating is
to provide corrosion protection to the aluminum alloy
and HSZ corrosion resistant coatings of several hundred
nanometers have been shown to provide adequate protec-
tion in corrosive environments [14]. The hybrid zeolite
coating thickness can easily be adjusted by altering the
LSZ seed crystal loading, more seed crystals results in a
thicker coating and less crystals result in a thinner coating.
Control of the synthesis time, which is the time that the
LSZ seeded substrate is in the HSZ synthesis solution, is
critical to produce a high-quality hybrid zeolite coating.
Synthesis times that are too short will result in poor adher-
ence of the hybrid layer to the HSZ-MFI coating because
the HSZ matrix surrounding the LSZ seeds will not be
 D.E. Beving et al. / Microporous and Mesoporous Materials 108 (2008) 77–85 81

Fig. 1. SEM images of zeolite coating on AA-2024-T3. (a) Top view of HSZ-MFI base layer, (b) cross-sectional view of HSZ-MFI base layer, (c) top view
of ZA seeded HSZ-MFI layer, inset is high magnification image of ZA crystals, (d) top view of hybrid layer, inset is high magnification image of hybrid
layer, (e) top view of hybrid layer on HSZ-MFI base layer after HF acid etching, and (f) tilted view of hybrid layer on HSZ-MFI base layer after HF acid
etching.

completely formed. Longer syntheses can generate hybrid
coatings enriched in HSZ and the HSZ may even mask
the LSZ if the synthesis duration is too long, decreasing
the hydrophilicity of the coating.
The XRD patterns (Fig. 2) confirm the type of zeolite
making-up each layer of the composite coating. The
XRD pattern for the MFI base layer on the aluminum
alloy (MFI/AA) is shown in Fig. 2a and the XRD pattern
for the ZA seed crystals is shown in Fig. 2c. The XRD pat-
terns for the ZA seed crystals and HSZ-MFI coating show
that both are pure phases with no other zeolites present.
Fig. 2b and d shows mixed phase XRD patterns with con-
tributions from both ZA and HSZ-MFI. Fig. 2b is the
XRD pattern of the MFI/AA seeded with ZA crystals
and Fig. 2d is the completed hybrid coating after the short
(4.5 h) hydrothermal synthesis of the ZA seeded HSZ-
MFI/AA in the HSZ-MFI solution.
The synthesis of the zeolite hybrid top layer is accom-
plished in two steps, similar to the seeded growth method
for generating zeolite coatings of a single zeolite phase.
The first step is the application of the zeolite seed crystals
to a substrate; here the substrate is HSZ-MFI coated alu-
minum alloy (MFI/AA). The second step is the immersion
of the seeded substrate into a zeolite synthesis solution and
hydrothermally treated. The seeded growth synthesis solu-
tions used for single phase coatings generally have chemical
compositions related to those used to synthesize the seed
crystals and will promote intergrowth and expansion of
the seed layer into a continuous pure phase coating during
hydrothermal treatment. The HSZ-MFI synthesis solution
82 D.E. Beving et al. / Microporous and Mesoporous Materials 108 (2008) 77–85

Fig. 2. X-ray diffraction patterns of the different zeolite crystal species and layers of the LSZ–HSZ composite coating. * denotes 2h peak from aluminum
alloy substrate. (a) HSZ-MFI coating on aluminum alloy, (b) HSZ-MFI coating on aluminum alloy seeded with zeolite A crystals, (c) powder zeolite A
crystals, and (d) completed hybrid coating.

used here as the seeded growth synthesis solution has a
chemical composition that is significantly different from
that used to synthesize the ZA seed crystals. The coating
that is generated after hydrothermal treatment of the ZA
seeded HSZ-MFI coated aluminum alloy is a hybrid zeolite
coating. This hybrid coating is a mixture of ZA and HSZ-
MFI. During the hydrothermal treatment in the HSZ-MFI
synthesis solution the ZA seeds do not enlarge and there is
no intergrowth of the ZA crystals, instead HSZ-MFI forms
around the ZA crystals embedding them in a HSZ-MFI
matrix adhering them to the HSZ-MFI base layer. The
hybrid coating is still highly crystalline as evidenced by
the XRD pattern (Fig. 2d) with its crystalline signature
contribution solely from ZA (Fig. 2c) and HSZ-MFI
(Fig. 2a).
Semiquantitative elemental analysis presented in Fig. 3
shows the different silicon-to-aluminum ratios between
the hybrid coating (Fig. 3b), ZA seed crystals (Fig. 3c)
and HSZ-MFI coating (Fig. 3a). HSZ-MFI has a much
higher silicon-to-aluminum ratio than ZA while the hybrid
coating has a silicon-to-aluminum ratio between that of ZA
and HSZ-MFI. After submersion in the 0.01 M silver
nitrate, the sodium ions in the pores of the composite coat-
ing are replaced by silver ions (Fig. 3d). It is the presence of
the silver ions in the pores of the composite coating which
confers the antimicrobial properties to the coating.
The hydrophilicity of the composite coatings was deter-
mined by water contact-angle measurements and compared
to the contact angles of pure phase ZA coatings on stain-
less steel (SS-304-2b) and HSZ-MFI coatings on aluminum
alloy (Table 1). The hybrid coating and pure ZA coating
have contact angles of zero and pure HSZ-MFI coating
has a contact angle of 30. There was no change in the con-
tact angle of the hybrid after it was ion exchanged with
silver.
The American Society for Testing and Materials
(ASTM) cross-cut tape test (D 3359-02 Method B) for
adhesion [10] demonstrates the strong adhesion of the
 D.E. Beving et al. / Microporous and Mesoporous Materials 108 (2008) 77–85 83

Fig. 3. Semiquantitative elemental analysis by EDS. (a) HSZ-MFI on aluminum alloy, (b) hybrid coating, (c) powder zeolite A, and (d) silver-ion
exchanged hybrid coating.

Table 1 greater than 1 · 106.5 CFU and incubated for 0, 4 and

Water contact angles on MFI, ZA, hybrid, and Ag-hybrid coatings 24 h. Each incubation time had six samples of silver-
Surface tested Contact angle () exchanged and six non-exchanged hybrid coatings. After
MFI on AA 30 incubation the E. coli were removed from the samples, pla-
ZA on SS304-2b 0 ted and incubated for 24 h for visual enumeration. The
Hybrid 0 enumerations after each incubation time yielded cell counts
Ag-hybrid 0 of greater than 1 · 106 CFU on the non-exchanged hybrid
coatings. By contrast, there were no surviving bacteria on
the silver-exchanged hybrid coatings. These results are sim-
hybrid coating to the aluminum alloy (Fig. 4). The hybrid ilar to those found by McDonnell et al. [4] and O’Neill
coating exhibited the highest adhesion rating of 5B. et al. [6] where the silver exchanged ZA coatings had little
McDonnell et al. showed that HSZ-MFI coatings on alu- or no surviving CFUs after the different incubation times.
minum alloys had adhesion ratings of 5B and ZA coatings The slight decrease in CFU on the non-exchanged samples
on stainless steel (SS-304-2b) had an adhesion rating of 4B observed between the 0 h and the 4- and 24-h incubation
[4]. The classification of the adhesion test results of 5B and periods is most likely due to the hydrophilicity of the
4B is characterized by having 0% and less than 5% removal hybrid coating. It is thought that hydrophilic coatings
of the coating, respectively [10]. If the hybrid layer is made may allow some of the bacteria to adhere to the coating
thicker by increasing the ZA loading, the adhesion rating instead of being transferred to the buffer solution for enu-
of the composite LSZ–HSZ coating becomes 4B (data meration [15]. This same trend was observed for the hydro-
not shown). When the thickness of the hybrid layer is the philic ZA coatings [4,6].
result of longer HSZ-MFI synthesis times (greater than The method of forming the zeolite hybrid layer demon-
4.5 h) the adhesion of the LSZ–HSZ composite coating strates great utility, virtually any zeolite combination of
remains at 5B (data not shown). zeolite seed crystals and zeolite synthesis solution can
Fig. 5 shows the anti-microbial efficacy of the silver- potentially be used to generate crystalline hybrid zeolite
exchanged hybrid coatings. Hybrid coatings were inocu- coatings. The function and application of these zeolite
lated with 500 lL of an E. coli suspension containing hybrid coatings is only dependent on the zeolite species
84 D.E. Beving et al. / Microporous and Mesoporous Materials 108 (2008) 77–85

Fig. 4. Polarized light microscope image of LSZ–HSZ composite coating on aluminum alloy tested for adhesion by ASTM standard D 3359-02 Method B.

Na Hybrid Ag Hybrid novel two-layer zeolite composite coating. The base layer
7
6
is a HSZ-MFI coating which can provide corrosion-resis-
tance if needed. The top layer is a zeolite hybrid coating
5
Average log cfu

made up of LSZ-LTA crystals embedded within an HSZ-

4
MFI matrix. The synthesis of the hybrid layer is achieved
3 by seeding the HSZ-MFI coated aluminum alloy with zeo-
2 lite A crystals followed by a short hydrothermal synthesis
1 in a clear HSZ-MFI synthesis solution. The short synthesis
0 is key to generating a functional hybrid coating with both
0 4 24 ZA and HSZ-MFI expressed on the surface of the hybrid
Incubation Time (hours)
coating. The purpose of the short synthesis is not to form
Fig. 5. Surviving colony-forming units (CFU) on hybrid coating and a PSZ-MFI structure but to use the short hydrothermal
silver ion-exchanged hybrid coating. synthesis to form a HSZ-MFI matrix around the ZA seeds
that adheres both the ZA seeds and the HSZ-MFI matrix
to the underlying HSZ-MFI coating. Because only a short
used to generate them. The LSZ–HSZ zeolite hybrid coat-
hydrothermal synthesis was performed the ZA crystals are
ing generated here functionally demonstrates features char-
still present at the surface of the hybrid layer, as such, their
acteristically limited to pure LSZ (zeolite A) and HSZ
hydrophilicity is accessible and can be exploited for their
(MFI) coatings. A pure ZA coating on stainless steel is
hydrophilic and antimicrobial potential. This is the first
extremely hydrophilic, easily silver-ion exchanged and
time that a purely crystalline, mixed zeolite coating made
exhibits an adhesion rating of 4B, whereas, a template-con-
from disparate zeolite species as a functional end product
taining MFI coating on stainless steel and aluminum alloys
has been generated. The zeolite hybrid coating demon-
is less hydrophilic, unable to be silver-ion exchanged and
strates great utility and its function and application can
exhibits the highest adhesion rating of 5B. We have suc-
be easily tuned by changing the zeolite species used to gen-
cessfully combined together the desirable properties of a
erate it.
LSZ and a HSZ into one hybrid coating, and thus opening
up many exciting possibilities for new applications.

5. Conclusions
The current work demonstrates, for the first time, the
formation of a hydrophilic and antimicrobial hybrid zeolite
coating on aluminum alloys. This was achieved through a
Acknowledgments
We acknowledge the financial support from the Strate-
gic Environmental Research and Development Program
of the Department of Defense (DoD/SERDP) and the Cal-
ifornia Space Institute.
 D.E. Beving et al. / Microporous and Mesoporous Materials 108 (2008) 77–85
References
[1] Y. Yan, H. Wang, Encyclopedia of Nanoscience and Nanotechnology
7 (2004) 763.
[2] Y. Yan, M.E. Davis, G.R. Gavalas, Industrial & Engineering
Chemistry Research 34 (1995) 1652.
[3] M.C. Lovallo, M. Tsapatsis, T. Okubo, Chemistry of Materials 8
(1996) 1579.
[4] A.M.P. McDonnell, D. Beving, A.J. Wang, W. Chen, Y.S. Yan,
Advanced Functional Materials 15 (2005) 336.
[5] R.A. Munoz, D. Beving, Y.S. Yan, Industrial & Engineering
Chemistry Research 44 (2005) 4310.
[6] C. O’Neill, D.E. Beving, W. Chen, Y.S. Yan, AIChe Journal 52
(2006) 1157.
[7] G.E. Totten, D.S. Mackenzie (Eds.), Handbook of Aluminum, vol. 1,
Marcel Dekker, New York, 2003.
85
[8] Y.S. Yan, D.E. Beving, High aluminum coatings on corrodible metal
surfaces, US patent 7,179,547, 2007.
[9] M. Smaihi, O. Barida, V. Valtchev, European Journal of Inorganic
Chemistry 24 (2003) 4370.
[10] D-3359-02 cross-cut tape test for adhesion, American Society for
Testing and Materials, ASTM, West Conshohocken, PA.
[11] M.M. Cowan, K.Z. Abshire, S.L. Houk, S.M. Evans, Journal of
Industrial Microbiology & Biotechnology 30 (2003) 102.
[12] X.L. Cheng, Z.B. Wang, Y.S. Yan, Electrochemical and Solid State
Letters 4 (2001) B23.
[13] D.E. Beving, A.M.P. McDonnell, W. Yang, Y.S. Yan, Journal of the
Electrochemical Society 153 (2006) B325.
[14] A. Mitra, Z.B. Wang, T.G. Cao, H.T. Wang, L.M. Huang, Y.S. Yan,
Journal of the Electrochemical Society 149 (2002) B472.
[15] H. Ai, Y.M. Lvov, D.K. Mills, M. Jennings, J.S. Alexander, S.A.
Jones, Cell Biochemistry and Biophysics 38 (2003) 103.