6

Cold spray process parameters: powders

F. J. B R O D M A N N, F. J. Brodmann & Co., USA

6.1 Introduction
The global powder manufacturing community is in the process of adapting
to increasingly challenging product requirements related to higher purity,
narrower particle size fractions, and controlled particle morphologies. The
major markets served by engineered powder products include the coating
industry, parts manufacturing, functional fillers, and powder coating applica-
tions. The cold spray process offers the opportunity to compete in all of the
listed product market segments. Functional fillers have been used in com-
bination with ductile matrix materials for cold sprayed coatings and net-
shape solid parts manufacturing.
The particle size specifications for cold spray powders range from nano-
size to over 400 micron (40 mesh). A powder particle size range of this
magnitude benefits the manufacturing yield for most powder production
processes. Within this range the ‘FloMaster’ cold spray powders exhibit a
very narrowly sized particle spectrum which aids in the cold spray produc-
tion of dense coatings and also wrought-like net-shaped parts. The required
particle size fractions are specific for each of the various cold spray and
kinetic spray equipment designs. The most frequently requested particle
size fractions are typically within the ranges of 5–25, 15–45, 63–90, 75–150,
and 200–400 micron particle diameter. The challenge for the powder manu-
facturer is to find customers for all powder fractions within the entire
spectrum of the particle sizes. The particle size range for ‘FloMaster’ cold
spray powders extends beyond the size distribution of the original feedstock
material produced by either atomization, friction alloying, vaporization, or
precipitation. The powder particle sizes are routinely increased by sintering,
fusion, and agglomeration and decreased by crushing, and ball or jet milling.
Process variations related to the choice of atomization gases, melting
temperatures, and processing time control the particle morphology.
Both the price and the output yield for cold spray powders are directly
related to the manufacturing yield which is a direct function of the particle

105
106 The cold spray materials deposition process

size and morphology specifications. Coarse metal powders in the 50–100

micron particle size range air atomized with irregular particle shape are
produced at the highest yield and lowest cost.

6.2 Selection criteria for cold spray feedstock

Starting in 1997, the first commercial orders for ‘FloMaster’ cold spray
powders were placed primarily from customers representing the automo-
tive parts industry, research institutions, and initial cold spray equipment
manufacturers. The early specifications criteria for cold spray powders were
limited to chemistry and particle diameter expressed in microns and/or
mesh size. The common test method for measuring the particle size of
powder products is ASTM B 214 using USA Standard E11 testing sieves
and a tapping sieve shaker. The particle size screening test also yields quali-
tative measures regarding the flowability of test powders. A quantitative
test method for powder flowability is ASTM B213 using a certified Hall
flowmeter. The equipment simultaneously measures the bulk density of the
test powder per ASTM B212.
Hall flow measurements together with bulk density tests were adopted
as standard quality control procedures for ‘FloMaster’ cold spray powders.
Comparing the flowmeter data from various cold spray powders indicates
that the flowrate is a function of the particle density, particle size and
particle shape. Micron-sized dense silver particles with spherical particle
morphology produced Hall flowrates in the range of less than 10 s/50 g.
Figure 6.1 illustrates the microstructure of 5–20 micron silver powder
atomized with nitrogen gas.

6.1 Scanning electron micrograph of nitrogen gas atomized silver

metal powder, 5–20 micron particle size.
 Cold spray process parameters: powders 107

The flowrate of a powder is an essential characteristic that determines

the feasibility for cold spray processing. Powders with flowrates above
60 s/50 g tend to build up and block the gas flow in the Laval subsonic and
supersonic nozzles. The early materials of choice for cold spray feasibility
evaluations were zinc, tin, aluminum, aluminum bronze, and copper powders
sized to −45/+15 micron with and without surface treatment. The surface
treatment was performed by annealing the powder in air using a time–
temperature controlled oven environment. Figure 6.2 shows air atomized
aluminum powder, 32–45 micron particle size, after annealing in air at
350 °F for 100 hours.
The chemical elements selected for cold spray processing have in common
low melting points and low resistance to deformation. The metal groups
meeting these properties include pure copper, silver, zinc, tin, bismuth,
indium, and aluminum and its alloys. These criteria are also met by high-
performance thermoplastic polymer compounds. The potential cold spray
polymer feedstock group is represented by high-density aromatic poly-
imide, aromatic polyester, polyetherketone, and high-temperature fluoro-
carbon resins. Figure 6.3 illustrates the microstructure of high-temperature
aromatic polyester, 45–100 micron particle size and angular particle
shape.
The thermoplastic polymer compounds are the common feedstock for
powder coatings using electrostatic or fluidized-bed coating methods.
During powder coating the parts are exposed to up to 450 °F in a curing
oven to melt the polymer powder on the part surface. Temperature-sensitive
material must be removed from the substrate before the start of the oven

6.2 Scanning electron micrograph of annealed air atomized

aluminum, 3600 ppm surface oxygen.
108 The cold spray materials deposition process

6.3 Scanning electron micrograph of aromatic polyester resin,

45–100 micron particle size.

curing cycle. Cold spraying of polymer powders eliminates the need for the
oven cure requirements.
The deformation and softening of solid matter is a function of tempera-
ture and the architecture of its structural building blocks such as crystal
structure and molecular chain length. Metals crystallize most frequently in
the cubic structure in either a face-centered or body-centered lattice. The
face-centered cubic-structured metals exhibit the lowest resistance to defor-
mation. The ASM Metals Reference Book1 lists the following metals with
face-centered symmetry: Ag, Al, Au, Cu, gamma Fe, beta Co, gamma Mn,
Ge, Ir, Ni, Pb, Pd, Pt, Rh, Si, and Sn. A comprehensive study investigating
the material characteristics for cold spray materials is outlined in reference
2. The report describes that cold sprayed ceramic feedstock was coated on
aluminum indicating that the properties of the substrate material must be
integrated in any cold spray coating feasibility study. In the example,
a brittle-phase ceramic material is bonded to a ductile metal substrate.
A test sample of cold sprayed aluminum metal on window glass prepared
by Anatolii Papyrin illustrates that a brittle substrate can be coated with a
ductile material.

6.3 Key powder properties

During the initial commercialization phase of the cold spray process involv-
ing equipment and process development, it became obvious to the applica-
tors that the feedstock powder properties are the most important variable
and require close control limits. Among the property variables, the particle
size of the powder is the most controllable. Commercial screeners using
 Cold spray process parameters: powders 109

vibration or tapping modes for the mesh screen sizes 40–635 mesh (20–425
micron) have an accuracy of ±0.5%. The subsieve (−635 mesh) fractions are
separated by water/air elutriators at an accuracy of ±10%. The material
properties that are the most difficult to control for cold spray powders are
the particle morphology and topography. The particle morphology affects
the Hall flowmeter measurements, bulk density, and screening results.
The spectrum of particle shapes includes perfect solid spheres, hollow
spheres, and near-spherical, dendritic, sponge, flakes, acicular, and fibrous
appearances. A powder composed of single-dimensional particles (spheres)
screens faster and at higher accuracy than a material composed of multi-
dimensional particles (acicular). The transformation from powder to cold
spray coating layer requires a minimum critical flight velocity of the particle
at the moment of impact with the substrate surface to facilitate cold weld-
type bonding. Assuming that the cold spray parameters are optimized, the
particle morphology and density affect the actual impact velocity, and sub-
sequently the coating density and deposition efficiency. In reference 3 the
critical velocities for cold spray powders were measured as a function of
particle size and particle temperature. It was observed that the particle
velocity decreases with an increase in particle diameter. Higher particle
temperatures associated with higher preheat gas temperatures resulted in
lower critical velocity requirements. An increase in particle temperature
ultimately leads to higher surface oxidation levels for non-noble metals.
High oxygen contents of the cold spray powder require in turn higher
critical velocities for coating formation.

6.4 Powder manufacturing process

The current consumption and production quantities for cold spray powders
indicate that the process remains in the experimental phase. Commercial
quantities of coarse tin and copper cold spray powders with spherical
particle morphology and low oxide content were quoted to automotive
customers. The most economical manufacturing process for powders suit-
able for cold spraying is atomization through a pressure nozzle using air or
inert gases. The formation of oxide layers on the surface of the molten metal
droplets during air gas atomization prevents the development of spherical
particles (Fig. 6.4).
The use of inert gases such as helium is required for the manufacturing
of spherical metal particles. The oxygen content of commercially produced,
passivated, −45/+15 micron-sized helium atomized aluminum is typically
2500 ppm; air atomized aluminum measures 2720 ppm; after annealing in air
for 100 hours the oxygen concentration increases to 3600 ppm. Figure 6.5
shows the microstructure of helium atomized aluminum powder containing
2500 ppm surface oxygen.
110 The cold spray materials deposition process

6.4 Scanning electron micrograph of air gas atomized aluminum

metal powder, −45/+15 micron particle size.

6.5 Scanning electron micrograph of helium atomized aluminum,

32–45 micron particle size.

Pure aluminum, silicon, tin, and zinc powders are classified as hazardous
substances by the US Department of Transportation (DOT) and are not
regulated after passivation by oxide surface coatings. This procedure
explains the small difference in oxygen content between helium gas and air
atomized aluminum powder. Copper metal has a high affinity for oxygen
and fine powder is safely produced in the submicron particle size ranges via
air or water atomization. Water atomized copper particles exhibit very
irregular morphologies from spheroidal to spongy. Figure 6.6 shows the
microstructure of water atomized high-oxide copper powder.
 Cold spray process parameters: powders 111

Low oxide containing copper powder for electronic applications is pro-

duced from air atomized feedstock via annealing in a hydrogen atmo-
sphere.4 The particle size yield for most metal atomization processes is
limited to particle sizes below 100 micron. Metal powders tailored for the
kinetic spray process require particle sizes up to 100 micron diameter. A
special agglomeration process using friction welding was developed to
convert a 100 micron powder to a 600–1400 micron powder. Figure 6.7
illustrates the morphology of friction-welded tin metal powder composed
of agglomerated particles.

6.6 Scanning electron micrograph of water atomized copper powder,

15–45 micron particle size.

6.7 Scanning electron micrograph of friction welded tin metal powder,

600–1400 micron particle size.
112 The cold spray materials deposition process

High-temperature flame and/or plasma processes are employed to

produce large-sized spherical particles from metal and ceramic feedstock.
Figure 6.8 shows the particle morphology of acetylene flame-treated
friction-welded, 60–90 micron particle size, steel powder.
At high scanning electron microscope (SEM) magnifications the steel
particles were identified as thin-walled hollow spheres. Potential applica-
tions for cold spray coatings composed of hollow metallic spheres made
from incramute and other alloys include acoustical and/or thermal insula-
tion products. A manufacturing process for aluminum powder composed of
hollow spheres is under development. Other particle morphologies such as
sponge and flake are commercially available for the fabrication of con-
trolled porosity and high-surface-area coatings or solids. Metal flakes and
sponge metals expose a higher surface area than spherical shapes and are
therefore classified as hazardous materials. To ensure the safe handling of
metal flake and sponge powders the particles are coated with organic liquids.
The same substances are also used during the ball milling process for the
production of flake powders. Commercially available metal flakes include
aluminum, chromium, copper, silver, and some of their alloys. Figure 6.9
shows the microstructure of metal flakes prepared from aluminum alloy
5056 using a high-speed milling process. Recently, stainless steel 316 has
been commercially produced as a flake powder for applications requiring
corrosion- and abrasion-resistant coatings.
The melting temperatures of refractory metals such as zirconium, hafnium,
tungsten, rhenium, tantalum, platinum, iridium, and other platinum group
elements exceed the limit for gas atomization. Refractory metal powders

6.8 Scanning electron micrograph of spheridized stainless steel

powder, 60–90 micron particle size.
 Cold spray process parameters: powders 113

6.9 Scanning electron micrograph of aluminum alloy 5056 flakes,

10–45 micron particle size.

6.10 Scanning electron micrograph of pure rhenium sponge metal

powder, 45–63 micron particle size.

are instead produced using hydrogen reduction and/or hydride/dehydride

processes. Current research in cold spray is aimed at extending its applica-
tion to refractory metals. Figure 6.10 exhibits the sponge structure of
hydrogen-reduced pure rhenium metal powder

6.5 New material developments

The worldwide materials industry has experienced a revolution related to
new materials and their commercial product applications. Three important
114 The cold spray materials deposition process

examples are the development of computer flat screens using indium-based

coatings, thin-film batteries using lithium-based electrolytes, and light emit-
ting diodes made from nano-sized titanate particles. The advanced materials
are mostly used as coatings to minimize material usage and space require-
ments. The cold spray process offers advantages to produce, with minimum
thermal exposure, coatings from functional materials such as thermo-
electric, magneto-caloric, photo-voltaic, piezo-electric, super-magnetic, and
high-temperature superconductive formulations.
Crystalline materials that experience phase changes as a function of
temperature, quasi-crystalline alloys composed of elements with very dif-
ferent melting points,5,6 and amorphous structures that crystallize during
temperature exposures are prime candidates for cold spray processing.
Brittle compounds such as carbides, nitride, silicides, borides, sulfides, and
ferrites have potential for cold spraying after the surface is coated with a
ductile-phase material. The resultant composite powder structure consists
of a core particle surrounded by a ductile coating of controlled thickness.
Commercial processes for particle coating are electroplating, electroless
plating, vacuum metalization, and cladding. The ductile coating layer for
surface bonding is formed from metals and metal alloys such as Al, Cu, Ni,
Co, Zn, Sn, Fe, and certain thermoplastic resins. The brittle-core material
choices include ceramic, glass, quasi-crystalline and amorphous structures.
Commercial applications have been established for composite powders
produced from nickel-coated hexagonal boron nitride, synthetic graphite,
bentonite, and other core materials.

6.6 Discussion
The emerging cold spray technology developed in two directions – one
emphasizing small particle diameters in the 5–40 micron range and the
other, described as kinetic spray, using larger particle diameter powders. In
both cases the powder particles are injected into a preheated gas stream
that propels the particles to supersonic speed before impact onto the sub-
strate surface. The required critical impact speed for larger particles is lower
than that for small particles, due to the higher temperatures that the larger
particles maintain. Improvements in deposition efficiencies were accom-
plished at higher gas temperatures, which in turn were responsible for
increased particle velocities. At gas temperatures above 375 °F the surface
oxygen of the metal particles and the exothermic reaction with non-noble
gases such as nitrogen or air further increase the particle temperature.
Higher temperatures improve the ductility for both the coating material
and the substrate, but might also lead to nitride and oxide formation in the
coating. The most reactive metals in contact with non-noble gases are Ti,
Al, Si, Mg, Hf, Zr, and Ta; and rare earth metals are classified as flammable
 Cold spray process parameters: powders 115

solids or spontaneously combustible. Aluminum metal particle surfaces are

customarily coated with a metal oxide layer to enable safe handling.
The behavior of the brittle oxide layer during impact with the substrate
is illustrated by a so-called ‘eggshell’ model. The ‘eggshell’ represents the
brittle phase in which the yolk substance is very ductile. During impact of
a raw egg with a hard surface the yolk separates from the eggshell. A similar
phenomenon is observed during impact of a metal particle that is coated
with a brittle oxide or nitride surface layer. At impact the brittle phase is
removed from the metal particle and exposes a clean non-oxidized surface
before cold welding to the substrate surface. Bond strength and deposition
efficiency measurements are required to quantify the function of the brittle-
phase coating thickness.
Improvements in bond strength and deposition efficiencies were also
reported for low-density metals such as aluminum, after the addition of a
high-density less ductile material such as steel to the ductile cold spray feed
powder. This so-called ‘hammer’ material is designed to increase the impact
energy for the low-density ductile phase without being deposited in the
coating layer. In addition the hammer material at certain concentrations,
particle shapes, and grain sizes performs blasting functions and removes
impurities from the substrate surface.
Developments related to the feedstock formulations are beneficial for
both the fine particle cold spray (5–45 micron) and the coarse particle (60–
90 micron) kinetic process. The manufacturing costs and safety concerns
for coarse metal powders are generally lower than for fine powders.
Micron-size fine powders must be annealed in air or nitrogen to ensure safe
handling during processing, shipment, and coating application.

6.7 Conclusions
Since 1997 cold spray coating technology has been emerging from the
research and development phase into limited and selective commercial
applications. Despite the long commercialization period, the industry
involved in Al, Cu, Zn, Sn, Ti, and Fe powder manufacturing remains opti-
mistic about large volume use of cold spray powders in automotive and
industrial product applications. The specifications for cold spray powders
should include parameters for particle size, particle morphology, and parti-
cle surface chemistry. Refinement in the powder manufacturing process and
subsequent treatments are required to meet the specification challenges for
commercially produced cold spray powders. Rising raw material costs – in
particular for Ni, Co, Mo, and Cu – and the more stringent powder process-
ing procedures at low manufacturing volumes are responsible for the high
cold spray powder costs. The high prices for metal feedstock equally affect
other coating processes such as thermal spray, electrolytic, and sputtering
116 The cold spray materials deposition process

processes. Industrial customers located in the Gulf Coast region are inter-
ested in cold spray for coating applications on large structures such as
bridges, tunnels, ships, floodgates, and marine platforms. The major concerns
related to the cold spray process are equipment availability, affordability,
and portability compared with coating methods currently employed.

6.8 Acknowledgments
The author thanks all customers of FloMaster cold spray powders for their
feedback especially Dr Anatolii Papyrin, Steve Johnson, John Potter,
Rick Blose, Daniel Gorkiewicz, Jerry Moleski, Phil Leyman, Dr Jegan
Karthikeyan, Dr Robert McCune, Robert Kasdorf, Wally Birtch, and
Carlos Henrique Santos. Many thanks to Dr Sandy Young of ARL,
Maryland, USA for the SEM photographs.

6.9 References
1 Gall T L (Ed.), ASM Metals Reference Book, Second Edition, 1982, ASM Inter-
national, Materials Park, Ohio.
2 Vicek J, Gimeno L, Huber H and Lugscheider E, A Systematic Approach to Mate-
rial Eligibility for Cold-Spray Process, Journal of Thermal Spray Technology, 14
(1), 2005, 125–133.
3 Li C-J, Li W-Y and Liao H, Examination of the Critical Velocity for Deposition
of Particles in Cold Spraying, Journal of Thermal Spray Technology, 15 (2), 2006,
212–222.
4 Yule A J and Dunkley J J, Atomizations of Melts for Powder Production and Spray
Deposition, Oxford Series on Advanced Manufacturing No. 11, 1994, Clarendon
Press, Oxford.
5 Sordelet D J, Besser M F and Anderson I E, Particle Size Effect on Chemistry
and Structure of Al-Cu-Fe Quasicrystalline Coatings, Journal of Thermal Spray
Technology, 5 (2), 1996, 161–174.
6 Goldman A I, Anderegg J W and Besser M F, Quasicrystalline Materials, Ameri-
can Scientist, 84, 1996, 230.