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Optimum Parameters for Wetting Silicon Carbide by Aluminum Alloys

Article  in  Metallurgical and Materials Transactions A · February 2000

DOI: 10.1007/s11661-000-0291-z

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Optimum Parameters for Wetting Silicon Carbide by
Aluminum Alloys
M.I. PECH-CANUL, R.N. KATZ, and M.M. MAKHLOUF

The effect of magnesium and silicon additions to aluminum, free silicon on the SiC substrate, nitrogen
gas in the atmosphere, and process temperature on the wetting characteristics of SiC by aluminum
alloys are investigated using the sessile drop technique. The contribution of each of these parameters
and their interactions to the contact angle, surface tension, and driving force for wetting are determined.
In addition, an optimized process for enhanced wetting is suggested and validated. Results show that
the presence of free silicon on the surface of SiC significantly reduces the contact angle between the
molten alloy and the substrate. The positive effect of silicon on the contact angle is attributed to a
chemical reaction in which both SiC and aluminum are active participants. The results also indicate
that nitrogen gas in the atmosphere positively influences the liquid/vapor surface tension, and the
presence of magnesium in the aluminum alloy favorably affects the overall driving force for wetting.
A mechanism is proposed to explain the beneficial role that the interaction of nitrogen with magnesium
plays in enhancing wetting. Magnesium significantly reduces the surface tension of aluminum melts
but has a low vapor pressure. Consequently, it readily volatilizes during holding at the processing
temperature and is lost from the alloy. It is proposed that a series of chemical reactions in the system
Al-Mg-N are responsible for reintroducing magnesium into the melt, thus, maintaining a low melt
surface tension. Interactions between the aluminum alloy and the silicon carbide substrate that may
lead to the dissolution of the substrate and the formation of undesirable reaction products, particularly
Al4C3, are examined, and means for mitigating their formation are outlined.

I. INTRODUCTION composites has also been introduced as a means of control-

SILICON carbide reinforced aluminum matrix compos-
ites have attracted considerable attention in recent years
because of their potential to exhibit enhanced mechanical
properties in comparison to the individual components, both
at room temperature and at elevated temperatures.[1,2,3] How-
ever, in order for these composites to achieve their full
potential, the SiC/Al interface must be carefully tailored so
that adhesion between the SiC and the aluminum alloy matrix
is strong. Optimizing the Al/SiC interface requires balancing
several process parameters. While a strong SiC/Al interface
may be created by promoting metallurgical bonding between
the SiC and the Al through interdiffusion and chemical reac-
tions, extensive interactions may result in degradation of the
SiC and reduction of the overall properties of the composite.
Moreover, because useful aluminum alloys contain elements
that have a high affinity for silicon and/or carbon, interfacial
reactions may occur and result in reaction products with
inferior properties. Most of the past effort dedicated to
improving the wetting of SiC by aluminum has centered
on modifying the aluminum with surface active alloying
elements and/or the SiC by surface coatings.[4,5] The use
of inert and/or reactive gases during the production of the
M.I. PECH-CANUL, formerly Graduate Student, Department of
Mechanical Engineering, Worcester Polytechnic Institute, is Researcher,
Center for Research and Advanced Sciences, Carr. Saltillo-Mty Km. 13
Saltillo Coah, Mexico, C.P. 25000. R.N. KATZ, Norton Research Professor
of Materials Science and Engineering, and M.M. MAKHLOUF, Associate
Professor of Mechanical Engineering and Director, Aluminum Casting
Research Laboratory, are with the Worcester Polytechnic Institute, Worces-
ter, MA 01609.
Manuscript submitted April 14, 1999.
ling chemical reactions and interactions at the Al/SiC inter-
face.[6] These efforts resulted in considerable improvements
in the properties of Al/SiC composites; nevertheless, Al/SiC
composites have yet to achieve their full potential. This is
attributed mainly to the lack of a quantitative understanding
of the effect of process parameters on the integrity and
strength of the Al/SiC interface. For example, it is well
known that Mg and Si additions to aluminum and nitrogen
gas in the furnace atmosphere[8] enhance the wetting of SiC
by molten aluminum. It has also been found that a thin layer
of Si deposited on the surface of the SiC improves the
spreading of molten aluminum on the SiC substrate.[7] How-
ever, the optimum amounts of Mg and Si in the alloy are
not known, and the role of nitrogen, and its interaction with
magnesium, is not clear. Moreover, wetting is a complex
phenomenon that depends on factors such as interface geom-
etry, process temperature, and soak time.
In this article, the effect of magnesium and silicon addi-
tions to aluminum, silicon coating on the substrate, nitrogen
gas in the atmosphere, and process temperature on the wet-
ting of SiC by Al alloys is investigated and quantified. The
optimum conditions for wetting SiC by aluminum alloys are
projected, and the wetting characteristics under optimum
conditions are determined and verified. Possible chemical
reactions and interactions at the Al/SiC interface are
identified.
II. BACKGROUND
Wetting is a term used to describe the distribution of liquid
on solids. Experimental measurement of wetting is most
conveniently based on the configuration of a steady-state
drop of liquid on a flat solid surface. This is referred to as

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 31A, FEBRUARY 2000—565


(a)
(b)
Fig. 1—Schematic diagram showing a sessile drop during (a) wetting and
(b) nonwetting.
a sessile drop. If the liquid drop is small enough that the
gravitational force is negligible relative to its surface tension,
the drop will attempt to assume a spherical shape because
it presents the smallest surface area, and, thus, the lowest
surface free energy. Cross sections of a sessile drop are
shown schematically in Figure 1. The contact angle, u, is
formed by the interface and a tangent to the drop’s surface
at its point of intersection with the substrate’s surface. The
surface tensions of the liquid/vapor, solid/vapor, and solid/
liquid are represented by the symbols glv, gsv, and gsl, respec-
tively. If the free energy of the solid is lowered when in
contact with a liquid, it will tend to be covered by the liquid
and is, thus, wetted. On the other hand, if the surface tension
of the solid is increased when in contact with the liquid, it
will tend to minimize the area covered by the liquid and is,
thus, not wetted by the liquid.
The solid substrate determines the configuration of the
sessile drop. When gsv is lowered by the presence of the
liquid, then a driving force equal to gsv 2 gsl will act on
the periphery of the drop and will extend the liquid/substrate
interface. This situation is depicted in Figure 1(a) and exists
when gsv . glv, gsv . gsl . glv, and u , 90 deg. A decrease
in the contact angle causes an increase in the drop’s surface
area and, thus, a decrease in the liquid’s surface free energy.
This is accompanied by a decrease in the solid’s surface free
energy. A balance of these two forces results in a steady-
state condition represented by an acute contact angle. Mathe-
matically, this balance is expressed by Young’s equation[9]
gsv 2 gsl 5 glv cos u [1]
The driving force for wetting is thus
Df 5 glv cos u [2]
566—VOLUME 31A, FEBRUARY 2000
When gsv , glv and gsv , gsl , glv (Figure 1(b)), a steady-
state condition arises with u . 90 deg. An increase in the
contact angle causes a decrease in the drop’s surface area
and, thus, an increase in the liquid’s surface free energy.
This is accompanied by an increase in the solid’s surface
free energy and a decrease in the wetting of the solid by the
liquid. The liquid-vapor surface tension may be determined
from the shape of the sessile drop using Eq. [3]:
glv 5
4
F
grd 2m 0.052
f
2 0.1227 1 0.0481f G [3]
where g is gravitational acceleration, r is density of the
liquid, dm is the maximum drop diameter, and f is a geomet-
ric factor.[10,11]
In both cases of an acute or obtuse contact angle, wetting
can be enhanced by a thermally activated chemical reaction
at the solid/liquid interface. However, reactions that enhance
the liquid/solid interface are the ones that contribute to the
driving force for wetting while creating minimum undesir-
able reaction products. Dissolution of a component of the
liquid into the substrate is an example of beneficial interface
reactions. In these reactions, the free energy of the reaction
at the perimeter of the liquid drop contributes to the driving
force for wetting. As the drop expands, the advancing liquid
maintains contact with unreacted solid, and thus, the free
energy of the reaction continues to contribute to the driving
force for wetting. Consequently, many research efforts have
been dedicated to designing alloys for use in metal matrix
composites incorporating elements that are capable of dis-
solving into the reinforcing ceramic at the process tempera-
ture.[12,13,14] Alloying elements also perform other functions.
For example, magnesium, which is one of the most com-
monly used alloying elements in aluminum/SiC metal matrix
composite alloys, acts as a powerful surfactant that scav-
enges oxygen. Magnesium forms MgAl2O4 spinel at the Al/
SiC interface. In addition to increasing the driving force for
wetting, this reaction consumes the oxygen present on the
surface of the reinforcement, thins the oxide layer, and,
thus, further enhances wetting.[15] Another commonly used
alloying element in aluminum/SiC metal matrix composite
alloys is silicon. It has been shown that an excess of silicon
in the aluminum alloy is favorable in retarding the dissolu-
tion of SiC by aluminum, according to the reaction[16,17]
4Al 1 3SiC } Al4C3 1 3Si
Therefore, silicon’s major contribution is not to wetting, but
rather to preventing the formation of Al4C3.
Research efforts have also been dedicated to enhancing
the wetting of SiC by aluminum through coating the SiC
with substances that are wet well by aluminum. For example,
it has been shown that coating the particles with K2ZrF6
causes a substantial reduction in the magnitude of the thresh-
old pressure required for infiltrating packed beds of the
particles with liquid aluminum.[18] It has also been shown
that coating SiC with Cu and Ni improves the SiC/Al inter-
face as reflected in improved mechanical properties.[19]
Moreover, it has been shown that aluminum alloys better
wet siliconized SiC substrates than unsiliconized SiC
substrates.[7]
METALLURGICAL AND MATERIALS TRANSACTIONS A
 Table I. Taguchi L8 Orthogonal Array Showing the Parameters Investigated
Number Mg N2 Mg 3 N2 Si Si 3 Mg Substrate Soak Temperature (8C)
1 ,0.01 0 — 0.1 — no Si wafer 1050
2 ,0.01 0 — 13.5 — with Si wafer 1235
3 ,0.01 100 — 0.1 — with Si wafer 1235
4 ,0.01 100 — 13.5 — no Si wafer 1050
5 9.00 0 — 0.1 — no Si wafer 1235
6 9.00 0 — 13.5 — with Si wafer 1050
7 9.00 100 — 0.1 — with Si wafer 1050
8 9.00 100 — 13.5 — no Si wafer 1235
Columns 4 and 6 are reserved for interactions between Mg and N2 and Si and Mg, respectively. In column 3, 0 denotes 100 pct Ar
during the entire test and 100 denotes 100 pct Ar during the heating period and 100 pct N2 during the isothermal period.

III. EXPERIMENTS C. Procedures

A. Design of Experiments Prior to each test, cubic pellets weighing 6 6 0.1 g were
cut from the cast alloy ingot and thoroughly polished with
The effect of the following parameters on surface tension 400-grit SiC paper. The pellets, the SiC substrate, and the
(glv), contact angle (u), and driving force for wetting (Df) was silicon wafer were ultrasonically cleaned in acetone
investigated: process temperature and atmosphere, substrate before use.
surface chemistry, and aluminum alloy chemistry—specifi- Tests were performed in a horizontal tube furnace with a
cally the alloy’s magnesium content and silicon content. 6.5-cm-diameter alumina tube that was closed at both ends
These parameters were chosen because of their perceived with end-cap fittings. A K-type thermocouple was inserted
substantial effect on the wetting of silicon carbide by alumi- in one end of the tube, while at the other end, an optical
num alloys. In order to reduce the number of experiments window allowed video recording and photography. Both
to a practical total, the Taguchi method for designing experi- end fittings were sealed with O-rings and are capable of
ments[20] was used. Each of these five parameters was used maintaining a vacuum of at least 3.5 3 1022 atm. The system
at two levels. In addition, those parameter interactions that was run at a very slight overpressure to ambient, and the
are perceived to have a significant effect on wetting of silicon test specimens were heated at a rate of 15 8C/min until the
carbide by aluminum alloys were included. Table I shows soak temperature was reached. Once the soak temperature
the five parameters investigated in this study arranged in a was attained, the specimens were held isothermally for 75
standard Taguchi L8 orthogonal array. minutes. During this isothermal period, the specimens were
photographed every 10 minutes to provide a record of the
change in the contact angle. Contact angles were measured
B. Materials from enlargements of these photographs. Surface tensions
The L8 orthogonal array shown in Table I requires four were determined using Eq. [3] and geometrical parameters
different aluminum alloys. The alloys were made from com- measured on photographs of the static interface obtained
mercially pure aluminum ingot, Al-Si master alloy, and Al- during the isothermal period. The driving force for wetting
Mg master alloy. The chemical compositions of the four was calculated using Eq. [2].
alloys used in this study are shown in Table II. In addition to measuring the contact angle and calculating
High purity flat, rectangular CVD silicon carbide sub- the surface tension and the driving force for wetting, the Al/
strates were used in the wetting experiments. The substrates SiC interface was carefully examined using scanning elec-
were 5 cm 3 5 cm 3 1.6 mm plates. When needed, a 0.28- tron microscopy (SEM) and energy disperssive X-rays
mm-thick electronic grade silicon wafer that represents 10 (EDX). Two types of specimens were prepared for optical
pct of the alloy’s weight was placed on top of the SiC and SEM examination: cross sections and “interface” speci-
substrate. mens. The interface specimens were prepared by carefully
removing the aluminum droplet from the silicon carbide
substrate by gradual mechanical polishing with 400-grit sili-
con carbide paper. All specimens were mounted and polished
Table II. Chemical Composition of the Alloys using standard metallurgical procedures. In addition, X-ray
diffraction (XRD) was used to identify reaction products.
Chemical Alloy 1 Alloy 2 Alloy 3 Alloy 4
Si 0.08 14.38 0.05 12.92
Mg ,0.01 ,0.01 8.86 9.28 IV. RESULTS AND DISCUSSION
Fe 0.2 0.16 0.09 0.18
Cu ,0.01 0.01 ,0.01 ,0.01 Analysis of variance (ANOVA) was performed on the
Zn ,0.01 0.02 0.01 ,0.01 data in order to identify the effect of each parameter and each
Ti ,0.01 0.01 ,0.01 0.01 interaction on u and glv and consequently on Df. Analysis of
Ni 0.01 0.01 0.01 0.01 variance provides insight into the optimum process parame-
Cr, Mn, Sn, Pb, Bi ,0.01 ,0.01 ,0.01 ,0.01 ters and allows estimating the magnitude of glv, u, and the
Al remainder remainder remainder remainder
driving force obtained when using the optimum process

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 31A, FEBRUARY 2000—567

 Table III. Pooled ANOVA Table for Contact Angle composition toward equilibrium, point B. Similarly, the liq-
uid becomes a participant in a reaction that changes its
Column Factor SS V P
composition toward point B. Figure 3 shows the dissolution
1 Mg 1711.130 1711.130 31 of silicon from the wafer into an aluminum alloy at the
2 N2 91.125 pooled — interface.* The contribution of the reactions to wetting may
3 Mg 3 N2 780.125 780.125 14
4 Si (in alloy) 45.125 pooled — *The silicon content of the alloy prior to the test was less than 0.1 pct.
5 Mg 3 Si 136.125 pooled —
6 Si (on SiC substrate) 2346.130 2346.130 42 be represented mathematically by modifying Young’s equa-
7 temperature 465.125 465.125 8 tion for a nonreacting, steady-state sessile drop (Eq. [1]) to
— error — — 5 include the contribution of the free energy of the reaction,
— total 5575.00 — 100 Fr:[21]
SS is sum of squares, V is variance, and P is percent contribution gsv 2(gsl 1 DFr) 5 glv cos u [4]
to the variance in surface tension. Mg 3 N2 and Mg 3 Si are the
interactions between Mg and N2 and Mg and Si, respectively. The Mg content of the alloy and the interaction of Mg in
the alloy with the nitrogen atmosphere also have significant
effects on u. One of the main functions of Mg as a surfactant
element is to reduce any aluminum oxide that may be present
in the melt, as well as that formed at the reinforcement
matrix interface.[15] The Al2O3 is thermodynamically stable
in contact with molten Al.[22] However, when the alloy con-
tains Mg, several reactions that may cause the reduction of
Al2O3 are possible; these include
3Mg (l) 1 Al2O3 (s) → 3MgO (s) 1 2Al (l)
Mg (l) 1 2Al (l) 1 2O2 → MgAl2O4 (s)
Mg (l) 1 4/3 Al2O3 (s) → MgAl2O4 (s) 1 2/3Al (l)
After each sessile drop experiment was completed and the
droplet cooled down to room temperature, the “skin” of the
droplet was removed with a clean sharp piece of CVD SiC
and collected as powder. The X-ray diffraction analysis of
these powders revealed the presence of a-Al2O3 in speci-
mens from runs that were carried out with a low Mg alloy
(runs 1 through 4). On the other hand, Al2O3 was not detected
in specimens from runs that were carried out with a high
Mg alloy (runs 5 through 8), confirming the role of Mg in
reducing Al2O3. Figures 4 and 5 are representative X-ray
diffraction patterns for both cases. The percent contribution
due to the error term provides an estimate of the adequacy
Fig. 2—Aluminum-silicon equilibrium diagram.[3] of the experiment.[20] If the error term is low, i.e., 15 pct or
less, it is assumed that no important factors were omitted
from the experiment, and no measurement errors were sig-
parameters. In addition, ANOVA provides a means of esti- nificant. On the other hand, if the percent contribution due
mating the percent contribution of each of the parameters to the error term is high, i.e., 15 pct or more, then some
tested to the variability in the measured quantities. important factors were omitted, experiments were not pre-
cisely controlled, or measurement errors were excessive.
The percent contribution due to the error term in this ANOVA
A. Contact Angle (u) is less than 5 pct, which indicates that no important factors
were omitted in the design of the experiment, and no mea-
Results of the pooled analysis of variance for u are shown surement errors were significant.
in Table III. The percent contribution (P) in Table III is Considering only the parameters and interactions included
an indication of the relative power of a parameter, or an in Table I in the ranges tested, the minimum u can be obtained
interaction, to affect variation in u. Table III indicates that, by using the process parameters shown in Table IV. When
at the levels studied, the process parameter that affects u using these process parameters, the projected contact angle
most significantly is silicon metal present on the surface of is 34 6 2 deg.
the silicon carbide substrate. Its relative contribution to glv
is about 42 pct. Silicon is expected to have a positive effect on
the contact angle. This may be best understood by referring to B. Surface Tension (glv)
the Al-Si binary phase diagram shown in Figure 2.[3] When Results of the pooled analysis of variance for glv are shown
a drop of liquid with the composition indicated by point C in Table V. Table V indicates that, at the levels studied, the
on the diagram is placed on a substrate with the composition process parameter that affects glv most significantly is the
indicated by point A, wetting occurs readily as the substrate presence of nitrogen in the atmosphere. Its relative contribu-
becomes a participant in a reaction that changes its surface tion to glv is 62 pct. The interaction of nitrogen with the

568—VOLUME 31A, FEBRUARY 2000 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 3—Optical photomicrograph showing Si particles from the silicon wafer dissolved in the aluminum droplet.

Fig. 4—X-ray diffraction pattern of powder removed from a droplet’s sur- Fig. 5—X-ray diffraction pattern of powder removed from a droplet’s sur-
face. The droplet did not contain magnesium. face. The droplet contained 9 pct magnesium.

magnesium content of the alloy also has a significant effect Table IV. Projected Process Parameters for Optimum
on glv. The percent contribution due to the error term in this Contact Angle
ANOVA is about 3 pct. It has been shown that magnesium Mg Alloy containing 9 pct Mg
additions to aluminum lower its surface tension[23] and its N2 0 pct N2 (only Ar)
work of immersion in SiC.[24] Consequently, aluminum Si in alloy 0.1 pct Si
alloys that are specifically designed for infiltration of SiC Si on substrate with Si wafer
Temperature 1235 8C
beds have invariably contained varying amounts of Mg.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 31A, FEBRUARY 2000—569

 Table V. Pooled ANOVA Table for Surface Tension
Column Factor SS V P
1 Mg 1800.0 pooled —
2 N2 140,980.5 140,980.5 62
3 Mg 3 N2 54,450.0 54,450.0 24
4 Si (in alloy) 14,280.5 14,280.5 6
5 Mg 3 Si 2450.0 pooled —
6 Si (on SiC substrate) 11,704.5 11,704.5 5
7 temperature 288.0 pooled —
— error — — 3
— total 225,953.5 — 100
SS is sum of squares, V is variance, and P is percent contribution
to the variance in surface tension. Mg 3 N2 and Mg 3 Si are the
interactions between Mg and N2 and Mg and Si, respectively.
Fig. 7—X-ray diffraction pattern of powder removed from the furnace
walls when the experiments were run under optimum conditions.

Fig. 8—X-ray diffraction pattern of powder removed from the surface of

Fig. 6—Gibb’s free energy change as a function of temperature for reactions the droplet when the experiments were run under optimum conditions.
occurring in the Al-Mg-N systems.[25]

Table VI Projected Process Parameters for Optimum

However, magnesium has a low vapor pressure and is, thus, Surface Tension
easily lost from aluminum alloys at elevated temperatures.
Mg Alloy containing 9 pct Mg
Al[Mg] → Al 1 Mg (g) N2 Ar → 100 pct N2*
Si in alloy 13 pct Si
The presence of nitrogen in the atmosphere, in addition to Si on substrate with Si wafer
minimizing oxidation of the substrate, helps reintroduce the Temperature 1050 8C
magnesium back into the melt. Figure 6 shows the Gibb’s
*One-hundred percent argon is switched to 100 pct N2 approxi-
free energy change vs temperature for reactions occurring
mately 5 min prior to reaching the isothermal soak temperature.
in the Al-Mg-N system.[25] Thermodynamically, formation
of Mg3N2 is favorable up to about 1100 8C and is
strongly exothermic:
2Al 1 Mg3N2 → 2AlN 1 3Mg
3Mg 1 2[N] → Mg3N2 1 DT
Al (l) 1 Mg (g) → Al[Mg]
Figure 6 also shows that AlN is more thermally stable than
Mg3N2 over the entire temperature range. Kinetically, how- Considering only the parameters and interactions included
ever, formation of Mg3N2 is more favored than formation in Table I in the ranges tested, the optimum glv can be
of AlN. During sessile drop measurements under optimum obtained by using the process parameters shown in Table
conditions, a greenish-yellow powder was always detected VI. When using these process parameters, the projected glv
on the chamber walls. The X-ray diffraction analysis of this is 420 mN/m 6 15 mN/m.
powder, shown in Figure 7, confirms it to be Mg3N2. Since
AlN is more stable than Mg3N2 above 1100 8C, molten
aluminum reacts with Mg3N2 to form the more stable AlN, C. Driving Force for Wetting (Df)
and magnesium is recycled back into the melt. Figure 8 Table VII shows the percentage contribution of each of
shows an X-ray diffraction pattern of powder removed from the process parameters and parameter interactions to Df.
the skin of the Al droplet, and it confirms the presence of Table VII indicates that, at the levels studied, the process
AlN on the droplet’s surface. parameter that affects the driving force most significantly

570—VOLUME 31A, FEBRUARY 2000 METALLURGICAL AND MATERIALS TRANSACTIONS A

 Table VII. Pooled ANOVA Table for Driving Force for
Wetting
Column Factor SS V P
1 Mg 176,489.29 176489.29 30
2 N2 45,222.27 45222.27 8
3 Mg 3 N2 19,840.32 pooled —
4 Si (in alloy) 478.02 pooled —
5 Mg 3 Si 14,582.90 14582.9 3
6 Si (on SiC substrate) 223,793.88 223793.88 38
7 temperature 87,279.06 87279.06 15
— error — — 6
— total 567,676.74 — 100
SS is sum of squares, V is variance, and P is percent contribution
to the variance in driving force. Mg 3 N2 and Mg 3 Si are the
interactions between Mg and N2 and Mg and Si, respectively.
Fig. 9—X-ray diffraction pattern of the Al/SiC interface showing the pres-
ence of Al4C3.

Table VIII Projected Process Parameters for Optimum

Driving Force
Alloy chemistry Al-13 pct Si-9 pct Mg
Substrate condition SiC with a thin silicon wafer on top
Temperature 1235 8C
Atmosphere 100 pct Ar → 100 pct nitrogen*
*One-hundred percent argon is switched to 100 pct N2 approxi-
mately 5 min prior to reaching the isothermal soak temperature.

is silicon coating on the surface of the silicon carbide. Its

relative contribution to the driving force is about 38 pct.
The Mg content of the alloy and the process temperature
also have significant effects on the driving force. The percent
contribution due to the error term in this analysis is approxi-
mately 6 pct.
Considering only the parameters and interactions included
in Table I in the ranges tested, the optimum driving force
can be obtained by using the process parameters shown
in Table VIII. When using these process parameters, the
projected Df is 437 6 15 mN/m.
D. Interface Reactions
Aluminum/silicon carbide composites are nonequilibrium
systems; consequently, chemical potential gradients exist at
the Al/SiC interface. These gradients are a driving force for
interfacial reactions that may occur during fabrication of the
composites at high temperatures. Although some interfacial
reactions are beneficial to wetting, others are detrimental.
At temperatures above the melting point of Al, and under
atmospheric pressure, SiC becomes thermodynamically
unstable and an invariant reaction occurs at 923 6 3 K and
leads to the formation of aluminum carbide (Al4C3).[16,26]
This is one of the most detrimental reactions that may occur
during the fabrication of Al/SiC composites.
4Al1 3SiC } Al4C3 13Si
Not only does this reaction cause the dissolution of the
SiC reinforcing particles and result in weakening of the
composite, but Al4C3 is also unstable and will react slowly
with atmospheric moisture to form aluminum hy-
droxide.[16,27]
Fig. 10—Optical photomicrograph showing the dissolution of SiC in the
Al alloy and the formation of Al4C3 at the interface.
Al4C3 1 12H2O → 3CH4 1 4Al(OH)3
Figure 9 shows the X-ray diffraction pattern of the Al/SiC
interface of specimen 5 (low Si alloy, no free Si on the
substrate’s surface, and high processing temperature). Figure
9 shows that, in this case, Al4C3 readily forms at the Al/
SiC interface. Figure 10 is an optical photomicrograph show-
ing the dissolution of SiC in the aluminum alloy at the
interface. Figure 11 shows the X-ray diffraction pattern of
the Al/SiC interface of specimen 6 (high Si alloy, free Si
on the substrate’s surface, and low processing temperature).
In contrast to Figure 9, Al4C3 was not detected at the Al/
SiC interface. Clearly, high levels of silicon in the alloy
coupled with a low processing temperature reduce the ten-
dency of the system to form Al4C3 at the interface. Another
potential reaction product in the SiC/Al system is the ternary
carbide Al4SiC4 that forms according to the chemical
reaction[17]
4Al 1 4SiC } Al4SiC4 1 3Si
The detrimental effects of both reaction products are com-
pounded by an alteration in the chemical composition of the

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 31A, FEBRUARY 2000—571


Fig. 11—X-ray diffraction pattern of the Al/SiC interface showing the
absence of Al4C3.
Fig. 12—Change in contact angle with time during the verification run.
alloy brought about by an increase in the Si content of the
alloy in areas adjacent to the Al/SiC interface. If the Si
content in these areas increases beyond the Al-Si eutectic
composition (12.6 wt pct Si), precipitation of primary silicon
particles may occur. These particles tend to degrade the
mechanical properties of the matrix alloy.
E. Verification of Projected Optimum Results
In order to verify the effectiveness of the projected opti-
mum conditions in producing enhanced wetting, glv and u
measurements were performed under the optimum condi-
tions shown in Table VIII, and the driving force for wetting
was calculated. Figures 12 and 13 show the change in contact
angle and surface tension with time during isothermal soak-
ing. The measured equlibrium contact angle is 31 6 2 deg,
the measured surface tension is 375 6 13 mN/m, and the
measured driving force for wetting is 330 6 12 mN/m,
which compare very favorably to the predicted values.
V. SUMMARY
The effect of magnesium and silicon additions to alumi-
num, free silicon on the SiC substrate, nitrogen gas in the
atmosphere, and process temperature on the wetting charac-
teristics of SiC by aluminum alloys was investigated using
the sessile drop technique. The contribution of each of these
parameters and their interactions, in terms of a relative
572—VOLUME 31A, FEBRUARY 2000
Fig. 13—Change in surface tension with time during the isothermal soak
period of the verification run.
power, to the contact angle, surface tension, and driving
force for wetting were determined. In addition, an optimized
process for enhanced wetting was suggested. Wetting experi-
ments were performed using the optimum conditions, and
the results show excellent agreement with projected values.
Results indicate that the presence of free silicon on the
surface of SiC significantly reduces the contact angle
between the molten alloy and the substrate. The positive
effect of silicon on the contact angle is attributed to a chemi-
cal reaction in which both SiC and aluminum are active
participants. The results also indicate that nitrogen gas as the
process atmosphere positively influences the liquid/vapor
surface tension, and the presence of magnesium in the alumi-
num alloy favorably affects the overall driving force for
wetting. A mechanism is proposed to explain the beneficial
role that nitrogen and its interaction with magnesium play in
enhancing wetting. Magnesium, which significantly reduces
the surface tension of aluminum, has a low vapor pressure.
Consequently, it readily volatilizes during holding at the
processing temperature and is lost from the alloy. It is pro-
posed that a series of chemical reactions in the Al-Mg-N
system are responsible for reintroducing magnesium into the
melt, thus, maintaining a low melt surface tension. Interac-
tions between the aluminum alloy and the silicon carbide
substrate that may lead to the dissolution of the substrate and
the formation of undesirable reaction products, particularly
Al4C3, were examined, and means for mitigating their forma-
tion were outlined. Elevated levels of silicon in the aluminum
alloy tend to decrease the incidence of aluminum carbide
formation.
The optimum conditions for wetting SiC by aluminum
that are described in this work were used to infiltrate SiCp
preforms, and the mechanical properties of the resulting
metal matrix composites were measured. Under optimum
infiltration conditions, metal matrix composites with less
than 3 pct porosity, over 200 GPa modulus of elasticity, and
about 300 MPa modulus of rupture were routinely
produced.[28]
ACKNOWLEDGMENTS
The authors gratefully acknowledge financial support
from the Fulbright-Garcia Robles Program, Materials and
Electrochemical Research Company, and the US Army
Research Laboratory.
METALLURGICAL AND MATERIALS TRANSACTIONS A
 REFERENCES
1. B. Maruyama: The AMPTIAC Newsletter, 1998, vol. 3, pp. 1-8.
2. S. Suresh, A. Mortensen, and A. Needleman: Fundamentals of Metal
Matrix Composites, 1st ed., Butterworth-Heinemann Co., Stoneham,
MA, 1993, pp. 3-22.
3. J.R. Davis: Aluminum and Aluminum Alloys, ASM Specialty Handbook,
4th ed., ASM INTERNATIONAL, Materials Park, OH, 1998, pp.
160-179.
4. F. Delannay, L. Froyen, and A. Deruyttere: J. Mater. Sci., 1987, vol.
22, pp. 1-16.
5. I.A. Ibrahim, F.A. Mohamed, and E.J. Lavernia: J. Mater. Sci., 1991,
vol. 26, pp. 1137-56.
6. M.K. Aghajanian, M.A. Rocazella, J.T. Burke, and S.D. Keck: J.
Mater. Sci., 1991, vol. 26, pp. 447-54.
7. M.I. Pech-Canul, R.N. Katz, and M.M. Makhlouf : Worcester Polytech-
nic Institute, Worcester, MA, unpublished research, 1998.
8. D.R. White, A.W. Urquhart, and M.K. Aghajanian: U.S. Patent No.
5,395, 701, 1995.
9. A.W. Adamson: Physical Chemistry of Surfaces, 1st ed., Interscience
Publishers, New York, NY, 1960, pp. 355-60.
10. L.E. Murr: Interfacial Phenomena in Metals and Alloys, 1st ed., Addi-
son-Wesley Publishing Co., Reading, MA, 1975, pp. 87-95.
11. T. Iiada and R.I.L. Guthrie: The Physical Properties of Liquid Metals,
1st ed., Clarendon Press, Oxford, United Kingdom, 1988, pp. 109-19.
12. V. Laurent, D. Chatain, and N. Eustathopoulos: J. Mater. Sci., 1987,
vol. 22, pp. 244-50.
13. J. Goicoechea, C. Garcia-Cordovilla, E. Louis, and A. Pamies: J.
Mater. Sci., 1992, vol. 27, pp. 5247-52.
METALLURGICAL AND MATERIALS TRANSACTIONS A
View publication stats
14. A. Alonso, C. Garcia-Cordovilla, E. Louis, J. Narciso, and A. Pamies:
J. Mater. Sci., 1994, vol 29, pp. 4729-35.
15. B.C. Pai, Geetha Ramani, R.M. Pillai, and K.G. Satyanarayana: J.
Mater. Sci., 1995, vol. 30 pp. 1903-11.
16. T. Iseki, T. Kameda, and T. Maruyama: J. Mater. Sci., 1984, vol. 19,
pp. 1692-98.
17. J. C. Viala, P. Fortier, and J. Bouix: J. Mater. Sci., 1990, vol. 25, pp.
1842-50.
18. A. Alonso, J. Narciso, A. Pamies, C. Garcia-Cordovilla, and E. Louis:
Scripta Metall. Mater., 1993, vol. 29, pp. 1559-64.
19. R.Y. Lin, R.J. Arsenault, G.P. Martins, and S.G. Fishman: Interfaces in
Metal-Ceramic Composites, TMS, Warrandale, PA, 1990, pp. 291-302.
20. R. Roy: A Primer on the Taguchi Method, Van Nostrand Reinhold,
New York, NY, 1990, pp. 40-75.
21. V. Laurent, D. Chatain, and N. Eustathopoulos: J. Mater. Sci. Eng,
1991, vol. A135, pt. 89-94.
22. R.L. Mehan and D.W. Mckee: J. Mater. Sci., 1976, vol. 11, pp. 1009-18.
23. John E. Hatch: Aluminum, Properties and Physical Metallurgy, 1st
ed., ASM, Metals Park, OH, 1984, pp. 208-9.
24. S.Y. OH, J.A. Cornie, and K.C. Russell: Metall. Trans. A, 1989, vol.
20A, pp. 533-41.
25. Q. Hou, R. Mutharasan, and M. Koczak: J. Mater. Sci. Eng. A, 1995,
vol. A195, pp. 121-9.
26. J.C. Viala, F. Bosselet, V. Laurent, and Y. Lepetitcorps: J. Mater. Sci.,
1993, vol. 28, pp. 5301-12.
27. T.Y. Kosolapova: Carbides Properties, Production and Applications,
1st ed., Plenum Press, New York, NY, 1971, pp. 250-4.
28. M.I. Pech-Canul, R.N. Katz, and M.M. Makhlouf : Worcester Polytech-
nic Institute, Worcester, MA, unpublished research, 1999.
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