DIFFUSION BRAZING OF AL ALLOYS FOR MICRO HEAT

EXCHANGER APPLICATIONS
E. R. Tagore*, B. K. Paul*
Industrial & Manufacturing Engineering
Oregon State University
Corvallis OR 97330

KEYWORDS rates. Even though, MECS could be fabricated

using cermic, metallic or polymer systems, for
Aluminium alloys, micro heat exchangers, heat exchanger applications metallic base
diffusion brazing. MECS are better suited. Thes devices generally
produced through microlamination techniques
ABSTRACT
involving the patterning, registration and bonding
Microfluidic devices are gaining its of thin materials sheets or laminae 14. Bonding is
importance over the years due to their ability to the final and important step in the fabrication of
operate at high diffusion rates especially in the MECS1. Diffusion bonding is widely used
area of heat transfer. Joining of these devices technique in which materials are joined together
without malfunctioning the base metal properties as the ultimate result of solid state diffusion
has been a challenging task for the researchers. phenomenon, occurring at relatively higher
This paper deals with the joining of aluminium temperatures (below the melting point) and
alloys (3XXX) for heat exchanger applications. pressures. It was reported that, this can be done
We aimed at developing a new technique, with or without the presence of intermediate
diffusion brazing or transient liquid phase layer (interlayer) which aids in the enhancing the
bonding of Al alloys using nano Ag coating as a diffusion rate2. Paul et al.15,23,13 demonstrated
braze filler. that arrayed microchannels of stainless steel,
copper and nickel aluminide can be packed to
I. INTRODUCTION form a microreactors and microcheatexchanger
devices through diffusion bonding. However
Microtechnology based Energy and diffusion bonding cycles are long and there are
Chemical Systems (MECS) are devices which issues with the reliability of the bonded joints. It
process bulk fluids in highly-paralleled arrays of also results in macroscopic deformation, also
microchannels. These arrayed channels enable called creep, in the devices due to applied
these devices to operate at shorter diffusional pressure at higher temperatures for long time.
distances, shorter resident time due to shorter These problems can be overcome by
channel lengths and thereby maintaining the introducing liquid phase during bonding which
pressure drop compared to bulk fluidic devices22. may require less pressure and results in
Synthesis of nano materials using MECS is one improved diffusion kinetics. One such technique
of the important applications and in this area is knows as diffusion brazing, it involves keeping
heat transfer is key step depending on whether it base metal with interlayer at particular pressure
is exothermic or endothermic reaction. Non and operated at higher temperature leads to
uniform heat transfer may lead to local formation of liquid phase either due to its low
overheated areas, so called hot spots and melting point or by forming eutectic with the
results in nano powders having wider size base metal. The applied pressure must not
distribution9. Micro heat exchangers serve the create any macroscopic deformation. Various
purpose of faster and uniform heat transfer theoretical models have been developed to
provide an understanding of the mechanisms shear strength of 75MPa when brazed with 3003
involved in forming diffusion braze. This Al alloy. Elsewhere, Suzuki et al.19 reported the
technique has been widely used for joining use of Zn alloying to reduce the melting
steels to a variety of materials such as Ti base temperature of the Al-Si filler and found out that
alloy1, Al base alloy16, Cu7 base alloy and low the eutectic Al-4.2Si-40Zn alloy can melt at
alloy steels. 535oC. However, the presence of Zn, lower
vapour pressure species, makes it unsuitable for
Aluminum by nature has light weight, good the vacuum brazing. Later, chauang et al.2
thermal conductivity and corrosion resistance designed a low melting filler using DTA
which make it as an ideal material for heat (differential thermal analysis) and found that Al-
exchangers. The presence of thin (~10A o), 7Si-20Cu-2Sn-1Mg can melt at 500oC. 6061-T6
adherent and native oxide (Al2O3) acts as a alloy when brazed with this filler alloy at 600 oC
diffusion barrier and prevents the formation of for 60 min and subjected to T6 treatment results
joint between any two Al arrayed micro channel in 196±19 MPa.
lamina21. One way to get away from oxide is use
fluxes containing F- ion which dissolves the Further developments in the brazing fillers
oxide and exposes nascent Al for bonding. lead to the invention of Ag-Cu system which has
Though it removes oxide completely, it eutectic temperature around 780 oC. In recent
contaminates the channels and not reliable to years, Lee et al.10,11 group has done extensive
use18. Other way is to do fluxless brazing in research in vacuum diffusion brazing of different
vacuum (1×10-5torr). In this fluxless brazing aluminium alloys with Ag-28Cu based brazing
oxide removal may happen by either of the fillers. One of the systems that they have studies
mechanism described below: is 6061 alloy with Ag-28Cu brazed at 450-560 oC
at a static pressure of 0.5MPa. From the DTA
1. Addition of little amount of gettering curves of 6061/Ag-Cu/6061 clad it was clear that
elements such as Mg which leads to the formation of liquid phase occurs at 492 oC.
formation of MgO, a thermodynamically Elsewhere it is reported that ternary alloy with
favorable phase than Al2O3. Al-Ag-Cu showed eutectic reaction at 500 oC.
2. During heating cycle, differential CTE The typical microstructure of the Ag-Cu bonded
between Al and its oxide may lead to aluminium alloy contains dark Cu-rich phase and
breakage of oxide layer. bright Ag-rich phase. The tensile strength of
3. Doping of filler metal with elements these joints brazed at 560oC for 30 min was
which can diffuse through oxide layer 160MPa. This observed inferior value indicates
and form liquid phase with Al. that elongated Cu-Al intermetallic phase causes
to decrease the strength. Similar kind of
Conventionally Al alloys are joined by deteriorating effect was reported by shin et al.20
fluxless brazing in vaccum. The most widely in case of Al6061 brazed joints. To improve the
used fillers are Al-Si8 and Ag-Cu10. In the case of strength further, T6 treatment was carried and
Al-Si, eutectic liquid forms at 577oC and forms a aging was done at 175 oC. Surprisingly, tensile
homogenous bond with Al. Although it forms a strength reached to 300MPa and the reason for
sound joint, brazing temperature is high relative the observed improvement was the diffusion of
to the melting point of pure aluminium (~660 oC), Cu-Al compound into base metal leaving
which degrades the mechanical properties of the homogenous and intermetallics free interface. It
base metal. Series of efforts were made to was also understood that Al5052 also behaves
synthesize the low melting filler materials. similarly when brazed with Ag-28Cu in vacuum.
Humpson et al.4 and Jacobson et al.5 developed
a filler metal having composition of Al-20Cu-2Ni- In spite of reaching mechanical properties of
5Si with a range of melting temperatures the base metal, for microHX, it is not beneficial
between 518oC and 538oC. They also realized a to use these conventional Al-Si and Ag-Cu
brazing foil materials. The laminae used for HX was mixed with 0.1ml surfactant (triton) and
is generally 50µm thick for which conventional added to 9ml of ethanol to make a solution of
foils would be too thick to use as a filler material
10% solid loading. This solution was kept in
and leaves extra material inside the laminae
features. The brazing temperature is also high
ultrasonicater for 1hr to get a homogenous
enough to cause significant creep in the device. solution. Similar procedure was followed to
prepare water base colloidal. Just before spin
Recent developments in nano technology coating, Al test coupons were cleaned in a
guided us to use the nano materials as the filler
standard acidic (2ml H3PO4, 1ml H2SO4 and 0.5
materials for diffusion brazing. Though it is
difficult to coat nano powders on laminae, we ml Triton, 96.5ml DI water) solution at 55 oC.
could get a micron level thickness. As the size of Later, all the samples were spin coated at
the particle decreases beyond certain critical 1000rpm for 30 sec using spin coater (XXXX).
value, due to increase in the surface-to-volume These coated samples were dried at 100 oC
ratio, the melting temperature deviates from bulk
before placing the stack in vacuum hot press for
and becomes size dependent property. Jiang et
diffusion brazing. All the experiments were
al.6 proved that nano Ag powder having 2nm
carried at a vacuum level ≥10 -6torr with constant
grain size can form liquid phase at ~200 oC
heating rate of 15oC/min and held for 30min at
compared to bulk melting point 962oC. Moon et
brazing temperature with 3MPa applied stress
al.12 investigated the sintering of silver nano
before cooling to down to room temperature.
particles (~20nm) using shrinkage with thermo
gravimetric analysis (TMA) and obtained 95% The coated films were annealed at different
density at a temperature of 250 oC. Elsewhere, temperature in vacuum and analyzed using
chou et al.3 studied the same but based on Scanning Electron Microscope (SEM) along with
conductivity of films. They found that the as coated condition. Differential Thermal
resistivity reached minimum for the films Analysis (DTA) was carried out for as received
sintered at 250oC and became insulating when nano Ag to identify any phase change. To
temperature was over 400oC due to silver characterize the joint, metallographic samples
coalescence into larger particles. It was also were prepared following standard ASTM
shown by puri et al.17 that Tm (melting procedures. The samples were mounted in
temperature) of nano Al decreases drastically epoxy resin and hardener (mixed in a 4:1 ratio)
from 660oC at 8nm to 200oC at 2nm. at room temperature and then kept for 18-24 hrs
to set. Mounted samples were sectioned using a
From the above findings, we expect that
diamond cutter (Buehler, 3.5” Diameter) and
nano Ag can form liquid phase at lower
polished using 120, 380, 600, 800 grit sand
temperature which can transport through oxide
papers respectively in DI water. In addition to
and forms eutectic liquid with Al which finally
this, cloth polishing was done using 5µm, 1µm
breaks the oxide layer. In addition to it, because
diamond suspensions and Al2O3 (0.05µm)
of its noble character, we can live away from
suspended in aqueous solution to get a scratch
oxide formation of fillers. The current study
free mirror finish. Optical microscopy was used
investigates the potentiality of using Nano Ag
to image the surfaces, bond lines and any
(<100nm) as a brazing filler for joining heat
surface defects. SEM with Energy dispersive X-
exchanger Al alloys at lower temperatures
ray spectrometry (EDS) was used to compare
II. EXPERIMENTAL APPROACH the microstructure and elemental composition
along the bond line to that of the bulk .
Initially the Al test coupons (McMaster-Carr,
US) of 1mm thickness were cut into 1”X0.5”
sizes and polished with 600 grid emery paper.
1g nano Ag (Sigma-Aldrich 99.9 % metal base)
III. Results and Discussions of grain coarsening due to Ostwald’s ripening.
Increase in Temperature also lead to formation
Figure 1 shows the DTA curve of as received of chemical bond, which is continuous and
nano Ag powder. DTA involves heating under contiguous [fig2 (d)].
identical conditions and measuring the
temperature difference between sample and
reference with respect to time. Two peaks are
easily seen from figure1.

0.1

0
Nano Ag
-0.1

-0.2
200nm
-0.3
Figure 2. SEM microstructure of nano Ag in (a) as
received (b), (c), and (d) were annealed at 125 oC, 275oC
-0.4 and 550oC respectively.
0 200 400 600 800 1000
Figure 3 shows the optical microstructures of the
Al alloys bonded without coating and with silver
Figure 1. DTA curve for the nano Ag in as-received
condition coating. All the samples were prior cleaned with
standard acidic solution [mentioned in section II].
It is reported in literature that nano particles
exhibit the surface melting phenomenon when Joint interface
the ration of surface atoms to bulk atoms is high.
We suspect the peak at 300 oC could be due to Figure 3. Optical micrographs of brazed joints at
formation of liquid phase on particle surfaces. To 500oC (a) no coat (b) Ag coat and 550oC (c) no
verify this spin coated films were annealed at coat (d) Ag coating.
different temperature and their morphologies The large no. of pores (dark dots) in the
were observed using SEM. aluminium (white phase) is inherited from the
processing stage. The Ag at the interface is in
Figure 2 show the morphology of films
solid state and it can also be attributed from
deposited on quartz plate and annealed at
DSC curve and the figure2. The pressure and
different temperatures. These SEM pictures give
temperature was high enough to form strong
no evidence of liquid formation or phase change.
neck growth and get sintered. From the
But, the morphology of powder annealed at
microstructures, it appears that all the samples
275oC shows the typical recrystallized structure
were bonded irrespective of the coating. But the
which can attributed to the second peak in the
microstructures do not have any kind of diffusion
DTA curve [figure 1]. From the figure (2), it is
zone which is typical characteristic of diffusion
also observed that the coating was uniform
bonding. To investigate the diffusion of elements
without any patches and agglomerations. The
into the bulk and join interface, EDS analysis
size distribution of as received particles is
was carried out on bonded samples.
narrow and the estimated average particle size
is ~50nm. From fig 2(a) to (d), as the annealing
temperature increases, there is clear evidence
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