USOO598.

5454A
United States Patent (19) 11 Patent Number: 5,985,454
McMOrdie et al. (45) Date of Patent: Nov. 16, 1999

54). ANTI-FOULING COATING FOR 5.242,488 9/1993 Stetson et al..

TURBOMACHINERY 5,279.650 1/1994 Stetson et al..
75 Inventors: Bruce G. McMordie, Perkasie; Mark OTHER PUBLICATIONS
F. Mosser, Perkiomenville, both of Pa. Lewis, “Hawley's Condensed Chemical Dictionary'', 12th
ed. Van Nostrand Reinhold Co., New York, p. 946 (1993).
73 Assignee: Sermatech International Webster's II, New Riverside University Dictionary, The
Incorporated, Limerick, Pa. Riverside Publishing Co. p. 916 (1984).
AMOCO Amide-Imide Polymers, Amoco Chemical Corpo
21 Appl. No.: 08/949,812 SR Sulli,ls
Cal TNO.
(Septegy
,353, rec' OV. ZO,
applicant in parent
22 Filed: Oct. 14, 1997 Corrosion Science, vol. 26, No. 9, pp. 727-734, 1986,
O O Mansfeld et al., Evaluation of Corrosion Protection Mea
Related U.S. Application Data Sures for Metal Matrix Composites.
63 Continuation of application No. 08/428,543, Apr. 25, 1995, Magnesium Elektron, Ltd., Brochure, pp. 3-14, Surface
abandoned, which is a continuation-in-part of application Treatments for Magnesium Alloys in Aerospace & Defence.
No. 07/861,328, Mar. 31, 1992, Pat. No. 5,409,970, which is Amax Magnesium document (34 pp.) Corrosion and Pro
a division of application No. 07/475,353, Feb. 5, 1990, Pat. tection of Magnesium.
No. 5,116,672. M. F. Mosser, “An Improved Coating Process for Steel
51 Int. Cl. .............................. B32B5/16; B32B 15/02; Compressor Components - Sermatel Process 5380 DP',
B32B 27/00 SAE Technical Paper Series, 24th Annual Aerospace/Airline
52 U.S. Cl. .......................... 428/413; 428/418; 428/461; Plating & Metal Finishing Forum & Exposition, Phoenix,
428/463; 428/469; 428/472.3; 428/472.2; Arizona, Apr. 4–7, 1988.
428/457; 428/458 Ronald Chow, Bruce McMordie, and Richard Wiegand,
58 Field of Search ..................................... 428/413, 457, “Performance Maintenance of Centrifugal Compressors
428/458, 418, 461, 463, 469, 472.3, 472.2 through the Use of Coatings to Reduce Hydrocarbon Foul
ing”, Elliot Company, Reprint: R-264, (1994).
56) References Cited Lee et al., “Handbook of Epoxy Resins”, McGraw-Hill
Book Co., New York, NY, pp. 2/4 & 4/59.
U.S. PATENT DOCUMENTS Department of Navy (MIL-M-45202B, Oct. 1968) docu
3.248,251 4/1966 Allen ....................................... 428/559 ment (35 pp.), Military Specification-Magnesium, Alloys
3.869,298 3/1975 Brumbaugh. and Anodic Treatment of.
4,097,445 6/1978 Martins et al.. Ministry of Technology (D.T.D. 911DC, May 1963) (7 pp.),
4,252,707 2/1981 Ruid. Process Specification-Protection of Magnesium-Rich
4,311,615 1/1982 Taylor et al. ........................... 252/514 Alloys Against Corrosion.
4,532,289 7/1985 Mosser et al. .......................... '"
4,537,632 8/1985 Mosser.
Amoco Chemical Corporation, Bulletin AM-1 (15 pp.),
4,554.213 11/1985 Marini. Amoco Amide-Imide Polymers.
4,606,967 8/1986 Mosser. Primary Examiner Donald R. Wilson
4,617,056 10/1986
4,650,819 Mosser. et al..
3/1987 Nakamoto A ttorney, A Fi Wei and ASSociates.
Agent, Or Firm-Weiser SOC1aleS, PC
P.U.
4,659,613 4/1987 Mosser et al. . 57 ABSTRACT
4,675,350 6/1987 Marchetti et al. ...................... 523/414
4,711,916 12/1987 Hagiwara et al. . Multilayered coatings comprising a Sacrificial primer layer,
4,724,172 2/1988 Mosser et al.. a non-Sacrificial Second layer, and a polymer topcoat are
4,806,161 2/1989 Fabiny et al.. disclosed
4,886,626 12/1989 Cope et al. ............................. 252/500
4,889,558 12/1989 Mosser .......... ... 428/457
5,116,672 5/1992 Mosser et al. .......................... 428/328 12 Claims, 1 Drawing Sheet
U.S. Patent Nov. 16, 1999 5,985.454
 5,985,454
1 2
ANTI-FOULING COATING FOR Polymerization fouling of aerodynamic hardware in cen
TURBOMACHINERY trifugal compressors pumping hydrocarbons reduces oper
ating efficiencies and component reliability. Though this
This application is a continuation of application Ser. No. problem has been known for years, relatively little work has
08/428,543 filed Apr. 25, 1995, now abandoned, which is a 5 been done to understand it and devise ways to minimize its
continuation-in-part of Ser. No. 07,861,328, filed Mar. 31, impact. The most probable reason for its lack of attention is
1992 (the "parent” application), which application issued as that fouling alone usually does not lead to a catastrophic
U.S. Pat. No. 5,409,970 on Apr. 25, 1995 and which is a machine malfunction or unscheduled downtime and can
divisional application of Ser. No. 07/475,353, filed Feb. 5, generally be handled by shortened maintenance intervals,
1990, which issued as U.S. Pat. No. 5,116,672 on May 26, where components are cleaned by removing accumulated
1992. polymer, returned to near original operating condition, and
put back into Service. These operations cause loSS of effi
FIELD OF THE INVENTION ciency.
The present invention relates to coatings that control Polymerization is not well understood, as it applies to
fouling that would otherwise compromise the efficiency of
15 compressor fouling. What is known is that the hydrocarbons
turbomachinery devices. which are inherent to the proceSS gas or formed during the
compression process can bond tenaciously to the component
BACKGROUND AND INDUSTRIAL base metals and lead to Significant performance loss of the
PROBLEMS machine. Deposits of this type have been found in compres
Sors used for hydrocarbon processing, coke gas blowers, and
Turbomachinery devices extract energy from moving other units where the gas contains Sufficient amounts of
fluids (air, combustion gases, water, Steam, etc.) or impart hydrocarbons under conditions of high pressure and tem
energy to those fluids. Under certain conditions, Solid mate perature.
rial can deposit from the fluids moving through the turbo Factors found to be critical to polymerization/fouling are:
machinery. At the very least, these deposits, generally 25
temperature-polymerization usually occurs above about
referred to as fouling, compromise efficiency by roughening 194° F (90° C.), pressure-the extent of fouling is propor
aerodynamic Surfaces. In the extreme, fouling deposits can tional to pressure level, Surface finish-the Smoother the
grow to fill internal passages, throttling flow. Surface the leSS apt the component is to foul, and gas
The precise nature of the deposits fouling a device will composition-fouling is proportional to concentration of
vary with the composition of the gas flow. For example, reactable hydrocarbon in the process (inlet gas).
organic polymers can deposit within units handling hydro In general, fouling has many detrimental effects on cen
carbon gases, while inorganic crusts form within turboma trifugal compressors. One is build-up of material on the
chinery operating on Wet Steam. In any case, efficiency is rotor. This build-up can lead to an unbalance which gradu
lost through three basic mechanisms: 35 ally builds until the unit exceeds its allowable vibration limit
Increased friction against gas flow, reduction of flow path and has to be shutdown. Operating with Significant rotor
croSS-Sectional area, and random changes of pressure dis unbalance can also lead to fatigue and a reduction in
tribution on airfoil. component life. Fouling has also been known to reduce axial
Polymerization is one type of fouling that plagues cen and radial clearances between the rotor and Stationary com
trifugal compressors pumping hydrocarbons in the proceSS 40 ponents which leads to abrasive wear that Severely damages
chemical and petrochemical industries. These chemical impellers and labyrinth Seals.
compressors deliver gases at Volumes, preSSures and tem These types of fouling degradation are typical of a pro
peratures critical to large Scale chemical processes. gressive formation of a deposit. Costs associated with cor
A centrifugal compressor acts on gas by means of a bladed recting these problems usually show up after relatively long
impeller. The rotating impeller imparts a centrifugal force on 45 periods of operation.
the process gas resulting in an increase of both its tangential However, polymerization fouling can occur So rapidly
and radial Velocity. The Velocity's tangential component is that efficiency losses occur very quickly, Sometimes only
then converted into an increase in pressure in the diffuser months after Start-up. In these cases, the most intense growth
passage of the diaphragm. The important individual aero of deposit occurs during the first 50-200 hours of operation.
dynamic components of a multi-State centrifugal compressor 50 The deposits affect Stationary flow path components, as well
include the inlet nozzle, inlet guide Vanes, impeller, radial as rotating elements. Prior attempts to correct the problem
diffuser, return channel, collector volute and discharge were limited to diffuser and return channels, Stationary flow
nozzle. path components, which were considered to be the most
The inlet nozzle accelerates the gas Stream into the guide Susceptible to fouling. It was assumed the rotating element
vanes which distribute the flow evenly to the first stage 55 would be less likely to foul due to the dynamic force applied
impeller. The rotating impeller forces the gas into the to the deposits by rotation. In addition, by design, the
diffuser formed by Stationary components called dia Stationary flow paths exhibit slightly rougher Surface fin
phragms. The diffuser reduces gas Velocity and converts ishes than the rotating element which make them more
kinetic energy in the Stream into higher preSSures. Because Susceptible to deposit build-up.
gas flows through the diffuser in a Spiral manner, it needs to 60 A different sort of fouling afflicts steam turbines. These
be straightened before it enters the next impeller Stage. This devices extract work from Steam Supplied from an external
is done by the use of return channel Vanes which are also part Source (boiler or process vessel). Steam, Superheated under
of the diaphragm assembly. It should also be noted that due very high pressures, enters the turbine and undergoes a
to the preSSure rise that is generated, the diaphragm is a controlled expansion as it passes over moveable and Sta
Structural, as well as an aerodynamic component. The col 65 tionary airfoils (blades and vanes). The force of the expand
lector volute and discharge nozzle reduce gas Velocity prior ing Stream causes the blades to rotate, doing work. AS the
to discharge. Steam expands, its temperature and pressure decrease until,
 5,985,454
3 4
in later Stages of the turbine, conditions are Such that it components in turbomachinery for over 25 years. The basic
Spontaneously condenses on gas path Surfaces. coating of this type has been described in U.S. Pat. No
The boundary between conditions of pressure and tem 3.248,251 (Allen). These coatings are complex water-based
perature in the Steam turbine that allow condensation and Slurries containing aluminum powder or alloy pigment par
those that do not is called the Wilson Line. Hardware ticles dispersed in an acidic Solution containing phosphates
operating well below the Wilson Line temperature and and hexavalent chromium ions which, upon exposure to heat
preSSure will be wet. Components well above this tempera and curing, transform to an insoluble metal/ceramic com
ture and pressure will remain dry. Since the Wilson Line will posite. Chromates (or dichromates), molybdates, vanadates,
move within the turbine as operating conditions and condi tungStates and other ions may be present. Commercial
tion of the inlet steam vary, some hardware will be alter examples of such a material include Alseal(R) 500 and 518
nately wetted and dried in Service. manufactured by Coatings for Industry (Souderton, Pa.),
When condensation occurs, impurities carried by or dis CT33 manufactured by Corrotherm Inc. (Croydon, Pa.), and
Solved within the Steam precipitate and deposit on the metal SermeTel W(R) and 962 manufactured by Sermatech Inter
Surfaces. The rough hard crust which forms compromises national Inc. (Limerick, Pa.). These materials continue to be
operating efficiency in the Same manner that polymerization 15 used in a wide variety of aerospace, automotive and indus
deposits compromise centrifugal compressors. Frictional trial applications. Coating compositions of this type con
resistance to gas flow is increased, croSS-Sectional area taining hexavalent chromium and phosphate are described in
available for flow is reduced, and variable pressure distri U.S. Pat. Nos. 3,248,249; 3,248,250; 3,395,027; 3,869,293;
butions are introduced in the unit. 4,537,632; 4,544.408; 4.548,646; 4,606,967; 4,617,056;
In addition to loSS of efficiency, fouling in Steam turbines 4,650,699; 4,659,613; 4,683,157; 4,724,172; 4,806,161;
also increases the risk of corrosion damage of components. 4,863,516; 4,889,558; 4,975,330; 5,066,540; 4,319,924 and
Condensing Steam is an electrolyte that can initiate galvanic 4.381,323, each of which (including the patent to Allen) are
corrosion on a Surface. This condition is exacerbated by incorporated herein by reference.
Sulfur and heavy metals, dissolved in incoming Steam, which After Such a slurry has been applied to a metal Surface,
25 usually by conventional air-atomized spraying, it is heated to
precipitate as hygroscopic Salts on airfoils. When operating
conditions change and Steam again condenses on these dried a temperature between 500 to 1000 F., preferably to about
Salts, extreme pH conditions (highly acidic for deposits of 343 C. (650 F) until cured. At these temperatures, the
acid salts, highly basic for basic Salts) results immediately phosphates and any other modifying ions, Such as
adjacent to the deposits. Severe corrosion, including pitting dichromates, undergo a Series of chemical reactions to
type corrosion, can result. Such corrosion not only roughens produce an inorganic amorphous glass matrix between the
airfoil Surfaces, but also compromises the mechanical integ aluminum pigmentation and between the coating and the
rity of the component. Substrate. Once cured, the Structure is frequently referred to
Corrosion fouling is not limited to Steam turbines. A as a "ceramic”, is water insoluble, and is tightly bonded and
Similar type of fouling can occur in centrifugal compressors very adherent. Tensile bond strengths of an aluminum-filled
35 chromate/phosphate on carbon Steel typically exceed 55
when there is significant moisture in the proceSS gas Stream.
Water that condenses from that gas collects on compressor MPa (8,000 psi).
components, leading to aqueous corrosion. Each aluminum particle in the coating is discretely Sepa
Some attempts have been made to address and Solve these rate from its neighbors. This discrete Separation, Visible in
industrial problems. To limit loss of efficiency due to fouling 40
the photograph, makes this coating a poor barrier and,
turbomachinery, various coatings have been formulated to though it contains about between 60-80%, or preferably
coat gas path Surfaces. It is desired that Such a coating should about 70%, by weight aluminum, this coating is not elec
have at least Seven characteristics as follows: be Smooth, trically conductive.
non-stick, unreactive, non-wetting, thin (less than 250 um or Sacrificial or "galvanic' electrically conductive coatings
0.010 inches thick), adherent, and be stable up to 260° C. 45 prevent corrosion by corroding in the place of the Substrate.
(500°F). When a metal that reacts more quickly in a particular
Several organic coating resins, including fluorocarbons environment (a more “active' metal) is placed into contact
such as polytetrafluoroethylene (PTFE), fluorinated ethylene with one that reacts more slowly (a more “noble” metal), the
propylene (FEP), and perfluoroalkoxy resins (PFA), or active metal will be entirely consumed by the environment
polyphenylene sulfides (PPS), are known to form smooth, 50 before the more noble material beings to corrode. A more
unreactive, non-Stick, non-wetting, thin films. However, galvanically active metal will corrode to protect a leSS
coatings of these polymers cannot be used on turbomachin galvanically active metal it when placed in a Saline envi
ronment. The more active metal is said to “sacrifice' itself
ery because the non-Stick materials do not remain bonded to for the more noble one.
iron, Steel and nickel alloy turbomachinery components in
Service. Additionally, Several of these fluorocarbons require 55 A number of engineering coating Systems are built around
a very high curing temperature, about 700° F (371. C.) for the Sacrificial principle. Galvanizing and Zinc plating, for
PPS and PTFE, which may adversely affect the mechanical example, use layers of active Zinc to Sacrificially protect
properties of the blades of the turbomachinery. Adhesion can Steels. Even if the Sacrificial Zinc layer is damaged, the
be improved by priming the metal with a mixture of resin active metal in the coating around the exposed Substrate
particles in an epoxy or other resin with a greater affinity for 60 corrodes, halting corrosion of that Substrate metal.
Steels. Better yet, a primer combining polymer particles in a Inorganic phosphates that are filled with pure aluminum
chromic acid slurry can be applied before the resin film. powder are galvanically Sacrificial when they are electrically
However, Such coatings have not proven to be Satisfactory as conductive. Such coatings can be made electrically conduc
no Such coating System adheres completely, and moisture tive by thermal or mechanical post treatments. Heating the
permeating the film corrodes the metal Surface below. 65 aluminum/phosphate glass composite to about 538 C.
Aluminum-filled inorganic phosphate overlay coatings (1000 F) causes the aluminum pigment and glass to react
have been used to combat corrosion and erosion of Steel and form a Semiconductor, AlP and the coating layer
 5,985,454
S 6
becomes conductive. Electrical resistivity of the coating turbomachinery, is galvanically Sacrificial and may or may
heated in this manner will drop to less than 15 ohms when not be conductive. This first layer preferably is an
measured with probes 1" apart. The same conductivity can aluminum-filled ceramic which contains inorganic phos
be achieved by lightly blasting the coated Surface with phate. The first layer may optionally contain additional
abrasive grit or glass beads. And when the aluminum-filled additives, Such as chromate or molybdate compounds, or the
inorganic phosphate is electrically conductive, it is also metal salts thereof. Alternatively to or in addition to
galvanically Sacrificial. aluminum, other particulate metals, Such as copper, Silver, or
For Some years it has been known to apply polymer films nickel or others listed in the Allen patent, may be included
directly on Sacrificial aluminum inorganic phosphate prim in the first layer. The first layer, in combination with the
other components of the coating of the invention, limits
erS. However, in Service, the life of these Systems on aqueous corrosion in moist environments Such as those
turbomachinery has always been compromised by Sponta within steam turbines.
neous delamination of the polymer film from the primer. In the coating of the invention, a Second layer is provided
These failures were caused by corrosion products which which is in contact with the first layer. The second layer is
formed at the interface between the primer and polymer 15
non-conductive and non-Sacrificial. To limit corrosion
Sealer. It had also been known to apply the polymer film between the layers of the coating, it is essential that the
directly onto the Steel Substrate material. Again, catastrophic Second layer be non-conductive. In one embodiment, the
failure occurred due to corrosion undercutting the film and Second layer is an inorganic material, Such as a phosphate or
delamination. During Service, moisture would permeate Silicate binder, lacking metal pigments. The Second layer
even the best organic Sealers. Corrodants dissolved in this may alternatively comprise metal particles, Such as
condensate would react with Sacrificial aluminum-filled aluminum, and/or other metallic pigments. In addition,
basecoat. Sacrificial products (like aluminum hydroxide) chromate or molybdate compounds, or the metal Salts
would form on the primer underneath the topcoat. AS these thereof, may be present. The Second layer may consist of an
products accumulated, the topcoat tends to blister and peel inorganic layer comprising fine inert pigments not reactive
from the Surface. This is especially true in the high StreSS, in acid binders, like thermally stable pigment Such as oxides
high erosion environment of turbomachinery. 25 of chromium (Cr2O), iron (for example magnesium ferrite,
MgO.F.O.), or aluminum, in a chromate/phosphate or sili
The parent application discloses a coating well Suited to cate binder. Alternatively, the Second layer may be produced
the coating of this invention which comprises a mixture of by hydrolysis of an organometallic, Such as aluminum
polyamide-imide, or epoxy/polyamide-imide, an ion reac isopropoxide, to produce an Al-O layer. The same modi
tive pigment and a leachable pigment, which coating cor fications described above for the first layer apply to the
responds to the third layer of the four layer coating of the second layer. When applied to the surface of the first
invention. conductive inorganic aluminum filled layer and cured, a
continuous thin film of non-conductive glass forms, Sealing
SUMMARY OF THE INVENTION the Surface and creating the desired non-conductive Surface.
The present invention relates to a composition of matter 35 The non-conductive Second layer may be produced on the
that is, a multilayered coating to control and to limit fouling Sacrificial first layer by applying and curing a Second coat of
of gas path metal Surfaces that would otherwise compromise the same inorganic aluminum phosphate as in the first layer.
the efficiency of turbomachinery. A third layer of an organic polymer Sealer is provided
The coating of this invention overcomes the limitation which is in contact with the second layer. The third layer
40 comprises a mixture of an organic polymer resin in an
inherent in non-Stick resin films by positioning an organic Solvent, which mixture may be referred to as a paint.
aluminum-filled inorganic phosphate or Silicate Sacrificial The resin bonds to the phosphate film of the second layer
primer between a polymer coating and the ferrous, nickel and, in a preferred embodiment wherein the Second layer
base or other metallic turbomachinery component. comprises particulate aluminum, anchors itself within the
The coating of this invention, comprising a passive inor 45 fine Surface pores of the aluminum-filled Second layer. In
ganic binder layer between a Sacrificial inorganic layer and one embodiment, the organic polymer resin is polyamide
an organic layer, overcomes the problem of delamination at imide or epoxy/polyamide-imide. The paint may contain a
the interface between the inorganic and organic layers of variety of additives and/or pigments, and may contain more
coatings used to prevent fouling and corrosion in turboma than one Solvent. For example, the third layer may contain
chinery. 50 an ion reactive pigment and/or a leachable pigment. The
Although reference in the invention is made to third layer, in combination with the other components of the
turbomachinery, it is contemplated that the coating of the coating of the invention, results in a coating that is durable
invention is also useful to protect other metal Surfaces which and will withstand the rigors of turbomachinery operation.
are exposed to conditions similar or less demanding to those A fourth layer, or top layer, is in contact with the third
to which the turbomachinery is exposed. 55 layer. The fourth layer is provided which comprises, in a
The resulting composite coating System, comprising a preferred embodiment, a mixture of polyamide-imide or an
Smooth, continuous organic film possessing a low coefficient epoxy/polyamide-imide and a fluorocarbon resin, Such as
of friction over a stable primer, remains tightly bonded to the polytetrafluoroethylene (“PTFE”) or fluorinated ethylene
iron, Steel, or nickel Substrates under the mechanical Stresses propylene (“FEP”), polyvinylidene fluoride, polytrifluo
of high Speed rotation, even in the presence of corrosive 60 rchloroethylene or other halogen-Substituted, preferably
electrolytes. The coating of this invention is particularly fluoro-substituted hydrocarbon polymers.
Suited, but not limited, to use on centrifugal compressors in In another embodiment, the invention is a multi-layered
hydrocarbon proceSS gas Streams and on Steam turbine coating for preventing fouling of turbomachinery which
components operating below or near the Wilson Line. comprises the first, Second, and top layerS described above,
One embodiment of the invention is a multi-layered 65 but which lacks the third layer.
coating for preventing fouling of turbomachinery. The first Another embodiment of the invention is a metal part
layer, which is in contact with the metal Surface of the coated with the multi-layered coating of the invention. A
 5,985,454
7 8
metal Substrate treated with the four-layer coating of the or chromium to inhibit the oxidation of metallic aluminum
invention will remain Substantially free from fouling and is obviated. The slurry may optionally contain magnesium.
corrosion after years of operation of turbomachinery at In 649, Stetson discloses that Small amounts of vanadium
operating temperatures, which typically are about 260 C. are necessary in the slurry. The first layer of the coating of
(500 F). This protection also results from treatment with the present invention, devoid of molybdenum or chromium,
the three-layer coating of the invention. may be formed in this way; however, it may also be formed
Another embodiment is a method of coating a metal part without equilibrating the aluminum, as required by Stetson.
with the multi-layered coating of the invention. The first layer is galvanically Sacrificial, that is, it is more
BRIEF DESCRIPTION OF THE FIGURES
active than the underlying Substrate and will corrode in place
of the less active, more noble Substrate. Thus, the Sacrificial
FIG. 1 shows a cross section of a preferred embodiment layer will protect the Substrate by corroding completely
of the four layer coating of the invention on a Steel Substrate. before the Substrate begins to corrode. The inorganic phos
The bottom layer 1 is a Sacrificial, inorganic aluminum phates and aluminum primer layer can be made galvanically
phosphate primer. The Second layer 2 is a non-Sacrificial, Sacrificial by making it electrically conductive.
15
inorganic aluminum-phosphate layer. The third layer 3 is a Alternatively, the first layer may be an inorganic phos
polyamide/imide layer containing aluminum, an ion reactive phate primer that is galvanically Sacrificial, but not electri
pigment and a leachable pigment. The fourth, top, layer 4 is cally conductive. An example of Such a Suitable primer,
a polyamide/imide mixture containing a particulate fluo comprising an inorganic coating containing finely divided
ropolymer. The three layer coating of the invention, con particulate aluminum alloys, particularly alloys containing
taining the bottom layer 1, the Second layer, 2, and the top magnesium, is described in Brumbaugh, U.S. Pat. No.
layer 4, lacks the third layer 3. 3.869,293, incorporated herein by reference. Because the
primers of the type described in U.S. Pat. No. 3,869,293
DETAILED DESCRIPTION OF A PREFERRED contain elements which are leSS noble than those found
EMBODIMENT OF THE INVENTION within the Substrate, they are galvanically Sacrificial, even
25
Coating of the Invention without being made conductive. Other suitable sacrificial
but non-conductive phosphate primerS may contain alloys of
The coating of the invention is a multi-layered coating aluminum and other active metals.
which prevents fouling on metal Surfaces in turbomachinery. PrimerS containing high levels of Zinc, are generally not
In one preferred embodiment, the coating is a four layer considered Suitable for the coating of this invention when
coating. used at high operating temperatures. Zinc is highly reactive,
FIG. 1 shows a cross section of a preferred embodiment and may thus cause catalysis of chemicals in the proceSS gas
of the coating of the invention. The first layer is a primer stream of turbomachinery. Further, zinc has a relatively low
layer, preferably between about 0.00125 to 0.00175 inches melting point of 293 C. (560 F). Because there is signifi
thick (32-44 um), in direct contact with and tightly bonded 35 cant diffusion of metals at temperatures above 0.8 of their
to the metal surface. This first layer preferably is an liquidus temperature, a primer having high levels of Zinc
aluminum-filled ceramic which contains inorganic phos would be limited to continuous operating temperatures of
phate and either chromate, or dichromate, or molybdate the equipment below about 149° C. (300 F).
compounds, or the metal Salts thereof. The aluminum in the The Second layer of the coating of the invention is an
ceramic is preferably in the form of discretely Separate 40 inorganic phosphate containing layer, preferably between
particles. A typical Suitable primer is described in Allen, about 0.00125 to 0.00175 inches thick (32–44 um), which
U.S. Pat. No. 3,248,251, incorporated herein by reference. may optionally comprise aluminum, chromate, or
Other metals may be present in the primer, as disclosed in dichromate, or molybdate compounds, or the metal Salts
Allen. Although Allen discloses an ideal size of 325 mesh thereof. In accordance with the invention, the first and
for the aluminum particulate matter, aluminum particles 45 Second layerS may contain common components, although
larger than 325 mesh are Suitable for use in the coatings of the concentrations and amounts of the components may
the present invention. differ between the layers. Alternatively, the components of
The aluminum particles may also be in the form of flakes the first and second layer may differ. For example, the first
or as a Spherical aluminum particles as disclosed for instance layer may contain chromate compounds, whereas the Second
in U.S. Pat. No. 4,537,632. 50 layer may contain molybdate compounds. The Second layer
Alternatively, the first layer may be an acidic phosphate/ may have any of the variants of the compositions as
chromate in which trivalent chromium has been Substituted described above for the first layer. In addition, the first or
for most or all of the hexavalent ion in the chromate/ Second layer may contain components not present in the
phosphate Solution from which the coating is made Such as other layer. Although not an essential feature of the
disclosed in Wydra, U.S. Pat. No. 3,875,717, incorporated 55 invention, in a preferred embodiment, the Second layer has
herein by reference. The first layer may also comprise an the identical composition as that of the first layer, the Sole
aluminum-ceramic formed from an acidic phosphate slurry difference being that the first layer is Sacrificial and the
from which hexavalent chromium or molybdate ions has Second layer is not. It is an essential feature of the invention
been Specifically excluded. Such coatings have been that the Second layer be non-conductive. The coating of the
described in Stetson, et al. in U.S. Pat. Nos. 5,242,488 and 60 invention, comprising a non-conductive Second layer
5,279,649, both of which are incorporated herein by refer between a Sacrificial first layer and an organic polymer
CCC. Sealer layer, has been unexpectedly found to resist corrosion
Stetson, in 488, discloses forming a slurry by the addition and delamination between the inorganic and organic layers
of Sufficient quantities of aluminum in a bonding Solution to of the coating.
equilibrate and to render inert aluminum in the bonding 65 The third layer of the coating is a passivating organic
Solution with respect to Subsequent additions of aluminum. polymer coating which is applied to the Surface of the
In this way, the need for environmentally toxic molybdenum non-conductive Second layer. The organic polymer is
 5,985,454
10
Selected to be Smooth, non-Stick, unreactive, and non mentioned ion and preferably a salt of limited solubility
wetting. Preferably, the organic film is Substantially imper typically strontium, Zinc, barium, potassium, Sodium,
meable to moisture and other liquids, especially at high calcium, lithium, magnesium.
operating temperatures, So as to improve resistance of the A preferred leachable pigment is a chromate-containing
coating to intermittent immersion. In addition, an organic pigment, preferably Strontium chromate, although any of the
polymer is Selected which is resistant to temperatures up to leachable pigments disclosed in the above-identified Mosser
260° C. (500 F). patent are Suitable, Such as Zinc chromate, Zinc
The third layer is a layer of a mixture of an organic tetraoxychromate, Zinc potassium chromate, barium
polymer dissolved or in Suspension in an organic or aqueous chromate, and barium metaborate. The third layer is pref
Solvent. In a preferred embodiment, the organic polymer is erably between about 0.00125 to 0.00175 inches thick
a polyamide/imide or epoxy polyamide/imide. Alternatively, (32-44 um).
phenolic polymers may be used in place of the polyamide/ It is not necessary that the third layer contain either one
imide. Other suitable polymers are disclosed in Mosser, U.S. or both of the ion reactive pigment or the leachable pigment.
Pat. No. 5,116,672, incorporated herein by reference. The fourth layer, which may be the top layer of the
Classes of polymers (and copolymers thereof) Suitable for 15
coating, comprises a mixture of an organic polymer in an
use in the coating of the invention include preferably hydro organic Solvent containing a fluorocarbon resin. Suitable
phobic or hydrophilic polymers which are thermally stable fluorocarbon resins include polytetrafluoroethylene or flu
at the operating temperatures of the turbomachinery. Such orinated ethylene propylene. In a preferred embodiment, the
polymerS may be thermosetting or thermoplastic, and organic polymer is epoxy/polyamide-imide, although any of
include, but are not limited to, polyolefins, copolyolefins, the polymers described above for the third layer may be used
ionomers, polyamides, copolyamides, halogenated as the polymer of the fourth layer. The specific nature of the
polyolefins, polyesters, unsaturated polyesters, Silicone top layer is not critical to the coating of the invention, except
polyesters, epoxy resin polymers, phenoxy (or phenolic) that it is essential that the polymer is thermally stable at
resins, alkyd resins, Silicone alkyd resins and acrylic resins. operating temperatures of the turbomachinery.
Specific polymerS Suitable for use in the invention include 25
but are not limited to the following: polyimide, In an alternative embodiment, shown in FIG. 2, the
polyethylene, polypropylene, polyphenylene Sulfide, poly coating of the invention comprises the first, Second, and top
Vinylidene fluoride, polyamide-imide, polyamide-imide layers described above, but lacks the third layer.
(epoxy modified), polyurethane, ethylene copolymers, eth The total thickness of the coating preferably is less than
ylene vinyl acetate copolymers, epoxy polyamide, polyvinyl 150 um (0.006 inches) so as not to reduce the cross sectional
chloride, polyvinyl fluoride, organosiloxane, polyvinylidene area available for gas flow, which would compromise the
chloride, polystyrene, polyacrylonitrile, cellulose acetate, efficiency of the turbomachinery. The coating also remains
polytetrafluoroethylene, fluorinated ethylene propylene, and tightly bonded to the Substrate throughout operation, even in
perfluoroalkoxy resins. the presence of aqueous electrolytes. Adhesion is not com
35 promised by impact of hard particles in the gas Stream or by
Preferably, the resin used will be able to be cured at a exposure to corrosive influences of the operating environ
temperature about 450 to 500 F. or lower. In one preferred ments. Finally, owing to the excellent thermal stability of the
embodiment, the resin is a polyamide-amide resin mixed coating, the coating of this invention can operate continu
with an epoxy resin, which mixture can be cured at a ously for extended periods of time at up to 260° C. (500 F)
temperature of about 300° F (149° C) or higher. 40 without loSS of physical properties.
Solvents (or liquids to disperse the polymer) which are Although a three and four layer multi-layer coating is
useful in accordance with the invention include but are not disclosed above, it will be understood by those skilled in the
limited to aliphatic hydrocarbons, aromatic Solvents, alco art that additional layerS may be added to the coating,
hols and other oxygenated Solvents, Substituted between the first and Second layers, between the Second and
hydrocarbons, phenols, Substituted aromatic hydrocarbons 45 third or top layers, between the third and fourth layers, or
and halogenated aliphatic hydrocarbons. Each resin has, as above the top layers without departing from the invention,
in known in the art, a group of Solvents and diluents providing Such additional layer(s) do not adversely affect the
compatible with the resin and suitable for film forming. In performance of the coating of the invention. The applicants
Some cases, the organic Solvent is used to disperse the resin rely on the doctrine of equivalents.
powder. It is contemplated that water can be used as Solvent/ 50
diluent or dispersant for certain resin pigment compositions. Method of the Invention
The third layer may contain one or more ion reactive The coating of the invention may be applied to a metal
pigments consisting of particles of any Suitable metal. Illus part by the method of the invention as follows. A slurry
trative of the class of metals are aluminum, magnesium, primer, preferably containing aluminum powder or alumi
Zinc, cadmium and other alloys. Magnesium/aluminum 55 num alloy pigment particles dispersed in an acidic Solution
alloys and alloys of the other above-mentioned metals are of phosphates, is applied to the Surface of the part. Other
included. U.S. Pat. No. 4,537,632 to Mosser and the metallic ions, Such as chromates, molybdates, Vanadates or tungStates
powders listed therein are incorporated herein by reference. may be present in the Slurry. Application of the primer is
The third layer may contain one or more leachable preferably by conventional air-atomized Spraying. Other
pigments consisting typically of a Salt containing chromate, 60 Suitable methods of application of the primer to the metal
molybdate, Vanadate, tungState, plumbate, phosphate or Surface include painting, rolling, brushing, dip/spinning, or
metaborate as well as others as listed in the publication by dipping.
Smith, entitled “Inorganic Primer Pigments”, Federation Following application of the primer, the metal Surface and
Series on Coatings Technology published by Federation of the primer is cured by heating to a temperature Sufficient to
Societies for Coating Technology, Philadelphia, Pa. (1988) 65 cause the phosphate and metal ions in the primer to produce
which is incorporated herein by reference. The cation of the an inorganic amorphous glass matrix between the aluminum
Salt can be any cation which forms a Salt with the above pigment and between the primer and the Surface to tightly
 5,985,454
11 12
bond the primer to the Surface. During curing of each layer, in the art that the various coatings illustrated can be modified
the layer dries. In a preferred embodiment, the temperature while being within the Scope and contemplation of the
is about 343° C. (650 F). The primer is then allowed to invention.
cool. EXAMPLE 1.
If desired, the primer layer can be made electronically A four layered embodiment of the coating of the invention
conductive by thermal or mechanical post treatments or any was installed in a cracked gas compressor. At this plant,
other suitable method. The primer layer may be heated to ethane is cracked to make ethylene and other hydrocarbon
about 540° C. (1000 F) which will cause the electrical by-products. Historical performance data showed compres
resistivity of the coating heated in this manner will drop to Sors fouled during operation. The operator washed the units
less than 15 ohms when measured by with probes 1" apart. with an oil Solvent to minimize fouling, Still it was desirable
The same conductivity can be achieved by lightly blasting to further limit the problem.
the coated Surface with abrasive grit, glass beads, or alu The shaft and impellers were thermally degreased at 650
a.
The Second layer is applied as a slurry over the cured F. (343 C.), then blasted to a gray metal finish using
primer layer and is cured using methods described above for 15 aluminum oxide grit. After removing dust and residual grit,
the first layer. The Slurry for the Second layer contains an 1 to 1.5 mils (25 to 37 microns) of a commercial chromate
acidic Solution of phosphates or Silicates. The Slurry may containing aluminum-filled inorganic phosphate coating
contain dispersed aluminum powder or aluminum alloy Slurry, as disclosed in Allen 251, was sprayed onto the parts.
pigment particles. Chromate or molybdate ions, as described After this coat was cured, the aluminum-filled inorganic
above for the first layer, may be present in the slurry. The phosphate primer was then lightly blasted with alumina grit
Second and Subsequent layers are not made electrically until it became electrically conductive and Sacrificial.
conductive. A second coat of 1 to 1.5 mils (25 to 37 microns) of this
A third layer is applied as an organic liquid composition Same coating was applied over this Sacrificial layer. This
Second coat was cured, but not made conductive, to effec
over the cured Second layer using methods described above 25 tively “bury' the first sacrificial layer of aluminum-ceramic
as for the first and Second layers. The liquid composition of coating. Then a layer of a coating comprising finely divided
the third layer contains a mixture a thermally stable organic aluminum and powdered Strontium chromate chemical in a
polymer in an organic Solvent. In a preferred embodiment, epoxy polyamide/imide resin binder, as described in Mosser
the polymer is polyamide-imide, epoxy/polyamide-imide, or (U.S. Pat. No. 5,116,672) was applied to complete the third
polyvinylidene fluoride. The composition may contain an layer of the coating system. This layer was cured at 375 F.
ion reactive pigment and/or a leachable pigment as (190° C) for one-half hour.
described above. The third layer is heated at a temperature Finally, the first three layers of the system were sealed
and time Sufficient to cure and to crosslink the resins of the
layer. In a preferred embodiment, the heat curing of the with a Sealer which comprises finely divided PTFE in the
epoxy polyamide/imide is at about 149° C. (300 F) to 190° epoxy polyamide/imide resin matrix as described in 672.
C. (375 F) for about 30 minutes. With a pure polyamide/ 35 The sealer was cured for 30 minutes at 375° F (190° C).
imide resin, the cure temperature is at about 260° C. (500 The total thickness of this system was 4.5 to 5.5 mils (115
to 140 microns), as measured by a magnetic coating thick
The top layer, comprising a fluoropolymer in an organic neSS probe.
polymer Sealer, is applied over the cured third layer using Performance of the compressor was monitored over the
methods described above as for the first, second, and third
40 17 months following installation of coating impellers. In that
layers. In a preferred embodiment, PTFE is incorporated as time, efficiency of the unit containing the articles of this
finely divided particles in a resin matrix organic polymer invention remained virtually constant compared to a 6%
Sealer, Such as a polyamide-imide or epoxy/polyamide reduction in efficiency during the previous run of the same
imide resin. The fourth layer is heated at a temperature and duration without coating on the impellers.
45
time Sufficient to cure the resin matrix, as for the third layer. EXAMPLE 2
In a preferred embodiment using an epoxy/polyamide-imide A chemical plant operating near the Gulf of Mexico in the
resin, the heat curing is at about 149° C. (300 F) to 190° continental United States was using a Steam turbine to drive
C. (375 F), or about 260° C. (500 F) for a polyamide centrifugal compressors in a proceSS gas train. The Steam
imide resin, for about 30 minutes. 50 turbine operated continuously for 16 years, during which
Alternatively, the coating may be applied omitting the time it was plagued by fouling by inorganic deposits from
third layer. The method of application of the first, Second, the Steam.
and top layers is identical to that described above for the At Overhaul, the condensation Stages of the unit Steam
coating comprising the third layer. turbine were coated with the coating of Example 1. The unit
The Coated Part of the Invention 55 was returned to Service, performance monitored and com
pared to its previous history. At Start-up, the turbine was
In accordance with the invention, metal parts which found to generate the same power as prior to overhaul while
benefit most from being coated with the composition taught consuming 5% less Steam. After 2 years in Service, the
in this application are those parts of machinery, particularly turbine was still using 5% less steam than it had before
turbomachinery, which are exposed at high temperatures to 60 overhaul to produce equivalent work. Boroscope inspection
gas flow and which, over time normally, become fouled by showed the coating of this invention remained intact on the
polymerization, Steam condensation, or corrosion. coated components. These Surfaces were largely clean and
In a preferred embodiment, the coated metal part is an free from fouling deposits that had been seen before the
iron, Steel, or nickel alloy machine component, particularly coating was introduced.
a turbomachinery component. 65 Other illustrations of the coatings of the invention can
The following examples are illustrative of the invention readily be devised by one of skill in the art from the
and are not meant to be limiting. It is evident to one skilled teachings presented herein.
 5,985,454
13 14
EXAMPLE 3 powder in an aqueous polyol was sprayed onto the
A carbon Steel panel was coated with the coating of aluminum-filled inorganic phosphate coatings on the Steel
Example 1, except that the epoxy polyamide/imide resin in Surface and allowed to dry. The coated part was then held at
the third and fourth layers was replaced with polyamide/ 370°C. (700°F) for 35 minutes to sinter the resin. After 500
imide resin. Because they lack the epoxy additives, these hours in 5% salt spray per ASTM method B117, the coated
organic layers were cured at 260° C. (500 F), instead of panel shows no red rust nor was there any evidence of
190° C. (375 F). The resulting coating was as smooth and blistering or delamination between the layers of materials in
the coating.
as fouling and corrosion resistant as that in Example 1 and
was harder and more erosion resistant. EXAMPLE 7
EXAMPLE 4 A cast iron plate was cleaned and then blasted with clean
aluminum oxide grit. An aluminum-filled chromate phos
A cast iron plate was cleaned and then blasted with clean phate coating of the type described in Allen 251 was applied
aluminum oxide grit. An aluminum-filled chromate phos to the blasted Steel Surface and cured by heating the part for
phate coating of the type described in Allen 251 was applied 15 30 minutes at about 343° C. (650 F). This aluminum-filled
to the blasted Steel Surface and cured by heating the part for ceramic coating was lightly blasted with alumina grit until it
30 minutes at about 343° C. (650 F). This aluminum-filled became electrically conductive. A Second layer of
ceramic coating was lightly blasted with alumina grit until it aluminum-filled chromate phosphate was then applied over
became electrically conductive. A slurry of the fine iron the conductive one. This layer was also cured 30 minutes at
oxide and titanium oxide powders in a chromate/phosphate 343° C. (650°F).
binder of the Allen type was then applied to Seal and A primer layer, as described in Example 1 of Mosser, U.S.
passivate the conductive aluminum-filled coating. This Pat. No. 4,5323,289, was applied on the cured aluminum
oxide-filled inorganic phosphate coating was cured 30 min filled inorganic phosphate. This primer was a slurry of fine
utes at 343° C. (650°F). particles of polyvinylidene fluoride resin in a chromate/
Subsequently, a primer layer comprising an epoxy amide 25
phosphate binder of the type described in Allen 251. This
imide resin with aluminum and chromate pigment coating was cured 30 minutes at 260° C. (500 F). A liquid
(described in Example 1) was applied onto the Sealed, Slurry of polyvinylidene fluoride resin was then applied over
passivated aluminum coating. A final Sealer comprising a the primer and cured to a uniform film at 288 C. (550 F).
mixture of PTFE in epoxy polyamide/imide resin (also The coated plate was placed in a fog of 5%. Salt Spray per
described in Example 1), was applied over the organic ASTM method B117. After 1500 hours, there was no red
primer layer. Both resin coatings were cured 30 minutes at rust nor was there any evidence of blistering or delamination
190° C. (375°F). between the layers of materials in the coating.
The coated plate was placed in a fog of 5% salt spray per It will be understood that various changes in the details,
ASTM method B117. After 1500 hours, there was no red materials, and arrangements of parts which have been herein
35
rust nor was there any evidence of blistering or delamination described and illustrated in order to explain the nature of this
between the layers of materials in the coating. invention may be made by those skilled in the art within the
EXAMPLE 5 principle and Scope of the invention as expressed in the
following claims.
A coil Spring made of high Strength low alloy Steel was 40
What is claimed is:
blasted with clean aluminum oxide grit. An aluminum-filled 1. A coating which comprises
chromate phosphate coating of the type described in U.S. a first cured layer of an adherent aluminum- or aluminum
Pat. No. 4,537,632 (Mosser) was applied to the blasted steel alloy-filled ceramic containing inorganic phosphate in
surface and cured by heating the part at 190° C. (375 F) for contact with a Surface, the first layer being either
24 hours. This aluminum-filled ceramic coating was lightly 45 (1) filled with an aluminum alloy or a pure aluminum
blasted with alumina grit until it became electrically con powder and having been made galvanically Sacrificial
ductive. A second layer of the slurry of Mosser 632 was and having an electrical resistance of less than 15 ohms
applied over the first conductive coat and again cured 24 measured with probes 1" apart,
hours at 190° C. (375°F). a Second cured layer in contract with the first layer, which
Subsequently, a layer of epoxy polyamide/imide resin 50 Second layer contains an inorganic phosphate or Silicate
coating (as described in Example 1) was applied on the binder and finely divided aluminum or aluminum alloy
non-conductive aluminum-inorganic phosphate coating. A powder which Second layer is not galvanically Sacrifi
non-Stick release coating, a mixture of PTFE in epoxy cial greater than 15 ohms measured with probes 1"
polyamide/imide resin (also described in Example 1), was apart, and
applied over the aluminum/chromate pigmented resin coat 55 a cured top layer which comprises a thermally stable
ing. Both resin coatings were cured 30 minutes at 149 C. organic polymer Sealer.
(300°F). 2. The coating of claim 1 in which the first layer is filled
The spring was placed in a fog of 5% saltspray per ASTM with finely divided particulate aluminum alloy which layer
method B117. After 2500 hours there was no red rust nor is galvanically Sacrificial to the metal Surface without being
was there any evidence of blistering or delamination 60 made electrically conductive.
between the layers of materials in the coating. 3. The coating of claim 1 in which the first layer has an
electrical resistance of less than 15 ohms measured with
EXAMPLE 6
probes 1" apart and is galvanically Sacrificial due to a
A carbon Steel panel was coated with the coating of post-thermal or mechanical treatment.
Example 1 except that the two final epoxy polyamide/imide 65 4. The coating of claim 3 in which the galvanically
layers were replaced with a single layer of polyphenylene Sacrificial property of first layer is imparted by the mechani
sulfide (PPS) thermoplastic resin. A suspension of PPS resin cal treatment.
 5,985,454
15 16
5. The coating of claim 3 in which the first layer has been 10. The coating of claim 1 in which the second layer is
Subjected to a post-thermal treatment. between about 32 to 44 um thick.
6. The coating of claim 2 in which the aluminum alloy is 11. The coating of claim 1 in which the organic polymer
an aluminum-magnesium alloy. Sealer is Selected from the group consisting of epoxy modi
7. The coating of claim 1 in which the first layer is fied polyamide-imide, polyamide-imide, polyphenylene Sul
between about 32 to 44 um thick. fide polytetrafluoroethylene, polyvinylidene fluoride, or flu
8. The coating of claim 1 in which the first layer contains orinated ethylene/propylene copolymer.
a compound Selected from the group consisting of chromate, 12. The coating of claim 1 wherein the coating comprises
molybdate, Vanadate and tungState, or the metal Salts an additional, thermally stable organic polymer layer, which
thereof. is Sandwiched between the Second and a cured top layer, and
9. The coating of claim 1 in which either or both of the is of a different composition than the top layer.
first two inorganic layers are free of molybdenum and/or
chromium Salts. k k k k k