Effect Of Grain Refiners and Nucleating

Agents on Mechanical Properties of Casting

Submitted By:
1. J. Sathish 18BME0482
2. Prakhar Chauhan 18BME0555
3. Vaibhav Mall 18BME0540
4. Akshay Raj 18BME0138
5. Snehanshu Suman Prasad 18BME2105
6. Vignesh Pathak 18BME0880
 OBJECTIVE

To do extensive study on the literature papers and

● The key methodology for this project study are: description and analysis.
● The collection of data from different research papers.
● The analysis of the experimental data and results. The properties affected by
the influence of the grain refiners and summary of the paper.
● This is entirely based on documentary analysis and data may include
research papers, journals, news articles, web content.
Literature Review:
 1. Past, present and future of grain refining of magnesium castings
Objective: To summarize the literature about grain refining of magnesium alloys focused on the (1) grain refining methods used in
the past, which are not used today, (2) grain refining methods currently being used in the industry and (3) novel and newly developed
methods that may find usage in the industry in future.

Methodology: Grain refinement of magnesium alloys:

● Past methods: 1. Superheating- Heating magnesium alloy melts above usual pouring temperatures (150 to 300 °C above liquidus
temperature) causes grain refinement in the cast products.

2. Native grain refinement- This effect only occurs in binary Mg-Al alloys. It is usually not possible to use high purity raw materials for
castings because of their higher cost, so this grain refining method cannot be used commercially.

3. Elfinal process (FeCl3 addition)- Addition of anhydrous FeCl3 to molten magnesium. The addition was made based on the
hypothesis that iron particles could act as nucleants for magnesium grains

● Present methods: 1.Carbon inoculation- Introducing carbon to molten magnesium can reduce the grain size. Carbon inoculation is
only efficient in magnesium alloys with aluminum addition (usually > 2% Al)

2. SiC addition- Although SiC particles have a different crystal structure (cubic) than Mg (hexagonal close packed), they have a
relatively low disregistry on close packed planes and directions. There are different explanations to the grain refinement mechanism of
SiC addition.

3. Zirconium addition- Zirconium forms stable compounds with these elements and cannot act as nucleant anymore. It has same
crystal structure as Mg (hexagonal close packed) and the lattice parameters of Zr ( a = 0.323 nm and c = 0.514 nm) are very close to
those of Mg ( a = 0.320 nm and c = 0.520 nm).
4. Effect of solute atoms- During solidification excess solute atoms that cannot be dissolved in the growing grains form a diffusion layer in the
solid/liquid interface. The built up of solute atoms causes a change in the chemical composition of the liquid ahead of the solidification front.

● Future methods: 1. Novel grain refiners for magnesium alloys- addition (or formation) of nonmetallic particles to the molten
magnesium.

2. Solute additions- Addition of solute elements with high GRF can cause a higher undercooling in the solid/liquid interface. This
higher undercooling can be effective to activate more particles to act as nucleants which results with finer grain size.

3. Agitation processes- Agitation of liquid metal (shaking, vibration, mechanical stirring, electromagnetic stirring or ultrasonication)
before or during solidification can refine grain size of the material. The main advantage of agitation processes is achievement of grain
refinement without addition of any alloying element or grain refiner particle.

Results: The efficiency of superheating also might be explained by the very prominent growth restriction factor of Fe itself. Even if the
solubility of Fe in molten Mg is low, up to 150–170 ppm can be picked up at elevated temperatures used for superheating.Although
FeCl3 is an efficient grain refiner for some magnesium alloys, Fe has a detrimental effect on corrosion resistance of magnesium alloys
[58–61] and release of Cl or HCl fumes during process causes environmental and health risks.Addition of 0.6 –1.0% of Al to Mg-10Y
alloy causes formation of Al 2 Y in the melt. This compound acts as a grain refiner and reduces grain size of the cast material from 180
to 36 μm.Addition of ZnO with a particle size of ∼200 nm to AZ31 causes grain refinement [128] . Although 200 nm ZnO particles are too
small to act as potent nuclei, reduction of ZnO to Zn solute causes grain growth restriction which results with finer grain size.

Summary: It is interesting that the mechanism of grain refinement in some methods that have been used for decades like carbon
inoculation or ultrasonic cavitation is still not clear. Different theories were reported by different researchers to clarify these situations.
The amount of research work done to understand existing grain refining mechanisms or to develop new grain refining methods for Mg
alloys increased continuously in the last two decades which is mainly a result of the demand for materials with higher specific strength to
obtain lightweight design in different applications.

Link : https://doi.org/10.1016/j.jma.2019.05.001
2. Effect of grain refiner on the tensile and impact properties of Al–Si–Mg cast alloys

Objective: Tensile and impact tests were conducted to evaluate the influence of the interaction between grain refiner
and modifier on the mechanical properties of the material. The properties were determined for both the as-cast and
heat-treated conditions.

Methodology: A356.2 Al alloy is used for the experiment. Variation of mechanical properties due to interaction of grain
refiner(Al–10%Ti, Al–5%Ti–1%B, Al–2.5%Ti–2.5%B, Al–1.7%Ti–1.4%B and Al–4%B as master alloys) and modifier(Strontium) by
adding them in various conc. Is observed.

Ti and B additions in the ranges of 0.02–0.5% and 0.01–0.5%, respectively whereas Strontium additions of 30 and 200 ppm were
made.

Experiment is carried out for as-cast as well as heat treated sample. Samples were first examined by optical and electron
microscope with EDX for determining grain size, WDS analysis provided chemical composition of intermetallics.

Then Universal impact testing machine is used to carry out impact tests on as-cast a well as heat treated specimen( heat
treatment at 540 ◦C for 8 h, followed by quenching in 60 ◦C water. The samples were then aged at room temperature for 24 h,
followed by artificial aging at 155 ◦C for 5 h, then air cooled).

The tests were conducted at room temperature at a strain rate of 2 × 10^−4 s−1. Tensile properties - ultimate tensile strength
(UTS), the 0.2% offset yield strength (YS) and percent elongation or strain to fracture (El.%) are measured.
Results:
On microstructure:

● Increase in the B-content beyond 0.1% leads to changes in the shape and size of the eutectic silicon particles, as was observed in the
microstructures of A356.2 alloy grain refined using Al– 2.5%Ti–2.5%B and Al–1.7%Ti–1.4%B master alloys.
● Addition of 0.1%B can be considered as the starting point for the transition of the eutectic Si particles in the modified alloy from fibrous
to coarse flakes.

Impact Properties:

● No significant variations in yield strength (YS) of the as-cast alloy are observed, regardless of the amount of Sr or grain refiner additions.
The T6-tempered alloys exhibit much higher YS values compared to the as-cast alloys.
● Under T6 temper condition, yield strength values of 30 ppm Sr-modified alloys are observed to decrease with the addition of
Al–2.5%Ti–2.5%B and Al–1.7%Ti–1.4%B grain refiners, while a rising trend is discernible for all grain refiner additions in the 200 ppm
Sr-modified alloy, particularly for additions of Al–10%Ti and Al–1.7%Ti–1.4%B.
● The T6 temper does not lead to any improvement in the elongation of the grain refined alloys compared to the as-cast condition, except
in the case when Al–4%B is used for grain refining.
● In the T6-tempered alloys, higher ultimate tensile strength (UTS) values may be obtained through the addition of lower amounts of the
master alloys, in the range of 0.02–0.04%Ti. Thus, it is important to select the appropriate grain refining agent in conjunction with the
appropriate amount of addition to maximize the alloy strength with respect to the applied heat treatment.

Summary: Addition of grain refiners to the metal casting can greatly improve the mechanical properties of the material by using
suitable type of master alloy and addition level of refiner. Grain refinement of the casting may also alter the amount and the
morphology of pores in the casting. We can change(increase or decrease) the mechanical properties of material by adding right
amount of grain refiner and modifier during casting. The impact properties of all tempered alloys are significantly higher than those
obtained in the as-cast condition.
Link for the paper: https://doi.org/10.1016/j.matdes.2013.11.058
3. Effect of iron on the microstructure and mechanical property of Al–Mg–Si–Mn and Al–Mg–Si
diecast alloys.
OBJECTIVE : To improve the tensile strength and reduce the ductility (mechanical property) of Al-Mg-Si based alloys to meet the
demand of thin wall casting in the application automotive structure. We study the effect of Fe (Iron) on the microstructure of the
alloy with different Mn (Manganese) concentrations that changes the mechanical properties to great extent produced by HPDC
process.The role of alloy chemistry on the effect of Fe and Mn was investigated by CALPHAD modelling of multi-component
Al–Mg– Si–Mn–Fe and Al–Mg–Si–Fe systems. The Fe rich alloys were studied with different concentrations of Mn in the alloy.

METHODOLOGY: The Al–Mg–Si alloys with different Fe and Mn contents were produced by melting the ingots of commercial
pure aluminum, pure magnesium and the master alloys of Al-15 wt%Si, Al-20 wt%Mn, Al-10 wt%Ti and Al-80 wt%Fe. Element
were weighed to a specific ratio with different extra amounts for burning loss compensation during melting. The 6–10 kg melt was
prepared in a clay-graphite crucible using an electric resistance furnace. The processing temperature of the melt ranged between
690 and 750C. Then the melted metal is fluxed and degassified with nitrogen gas for 3 minutes.

● COMPOSITION ANALYSIS: The melted metal was then pour into steel mould and bottom ground to 800 grit abrasive
paper. The composition of each alloy was obtained from an optical mass spectroscopy, in which at least five spark
analyses were performed and the average value was taken as the chemical composition of alloy. The composition was
further confirmed by area Energy Dispersive X-ray (EDX) quantification in SEM.
● TENSILE TEST: After composition analysis and skimming, the melt was manually dosed and subsequently released into
the shot sleeve of a 4500 kN HPDC machine for the final casting. The casting die was heated by the circulation of oil at
250C. All castings were kept at ambient condition for at least 24 h before the mechanical property test.Six ASTM standard
samples with three dia 6.35 mm round bar and three square bar were cast in each shot. Tensile test were conducted in the
ambient temperature i.e 25C.
RESULT: In HPDC of f Al–Mg–Si–(Mn) alloys, the formation of Fe-rich intermetallics occurs into two solidification stages.
One is in the shot sleeve at lower cooling rates, and the other is in the die cavity at higher cooling rates. The Fe-rich
intermetallics formed in the shot sleeve exhibit needle shape while intermetallics formed in die casting have fine structure
of size less than micrometer.

Fe-rich intermetallics significantly affect the mechanical properties of the alloy castings. The higher the iron
concentrations in the alloy, the more significantly the ductility reduces. This is accompanied by a slight enhancement of
the yield strength. Fe content ranges from 0.21wt% to 1.24wt% and the alloy precipitates either to form coarse compact
in shot sleeve or fine particles in diecast cavity. The detrimental effect of iron content on the mechanical properties in the
diecast Al–Mg–Si alloys is mainly due to loss in ductility but on the other hand Mn has slightly increased ductile nature
due to the morphologies and size of Fe intermetallic microstructure. However, we have seen that the ductility also
diminishes with increasing the Fe content above 1.2wt%. It all depends on cooling rate where lower cooling rate in sleeve
forms compact structure while higher cooling rate in die cavity causes formation of fine compact structures. The overall
increase of the yield strength of the Al-Mg-Si diecast sample was 8% while the ultimate tensile strength decreased by 9%
and the elongation decreased by 295%.

SUMMARY: We have seen how the mechanical properties of an alloy can be varied according to our need and
requirement. In this research paper we have used the iron and small concentration of manganese to reduce the ductility
and improve the tensile strength of our diecast alloy for better casting.We saw the microstructure and property
relationship in terms of grain refiners used with their concentration. Grain refinement techniques results in finer grains
and enhanced surface finish which not only helps in better castibilty but also ensures low density of alloy which can used
to produce components, parts, systems of automotive and aerospace industries.
Link of the paper : https://doi.org/10.1016/j.msea.2012.11.095
 4. Effect of erbium addition on Al-Mg-Mn-Zr Alloys
Objective: To study the methodology and effects of erbium addition on Al-Mg-Mn-Zr alloys.

Methodology: Effect of erbium As-cast microstructure

● Addition of 0.2 wt.% Er does not result in grain refinement.However, there does seem to be a refinement of the dendritic
substructure within the grains
● Addition of 0.4 wt.% Er, the grain size reduced significantly. The grain size of the alloy with 0.4 wt.% Er is only half of that 0.2 wt.
%.Further increase of Er only leads to a slight decrease in grain size
● The grain size of the alloy with 0.6 wt.% Er is close to that of the alloy with 0.4 wt.% Er
● Addition of 0.4 wt.% Er, which is less than the binary Al–Er eutectic composition of 6 wt.%, refines the grain size of the as-cast
alloy relative to that of the Er-free alloy. The grain refinement is accompanied by formation of primary Al3Er at grain boundaries
,which indicates that prohibition of primary Al3Er on grain growth leads to the grain refinement

Homogenized microstructure

Cast alloys have the dendritic structure with solute atoms segregating at the inter dendritic regions, so they must be
homogenized to obtain more uniform properties. During homogenization, the solute atoms dissolve into the inner-grain regions,
and the dendritic structure disappears. 0.2 wt.% Er dissolved in the Al matrix, and the other excess Er atoms segregated to form
the primary Al3Er phase at grain boundaries during solidification . Differential scanning calorimetry (DSC) measurements of the
cast alloys show that primary Al3Er does not decompose when the temperature approaches the melting point of the
corresponding The solid solution decomposes to form a dispersion of secondary Al3Er during homogenization at 470 alloy. The
HRTEM image shows that the precipitate is coherent with the matrix and has facets parallel to the {100} and {110} planes. Some
Al3(ErxZr1−x) precipitates with a cuboidal morphology also form in the alloys with addition of Er, and their particle size is
relatively smaller than for Al3Er.
Results: erbium on mechanical properties

Addition of Er leads to improvement of mechanical properties due to formation of secondary Al3Er

Link: https://doi.org/10.1016/j.msea.2009.02.045
 5. Influence of yttrium on microstructure as-cast Mg–5Li–3Al–2Zn alloy
Objective: To study the influence of yttrium on microstructure as cast Mg-5Li-3Al-2Zn alloy.

Methodology: Effect of grain size due to Y additions

the alloys were treated with solid solution.

The addition of Y has a refining effect on the grain size .In more detail, the best refining effects obtained when Y contentis 0.8 wt.%

many black spots occur in the alloys after solid solution; the high magnification images of the alloy are observed using SEM to further
reveal the spots

From the SEM image of LAZ532 alloy (Fig. 4), almost all the spots are gas pores which possibly form during the solid solution
treatment. However, from the image of LAZ532–0.4Y alloy

very few gas pores, many small particles, which are rich in Al and Y, are dispersed in the alloy.

Phase composition of alloys

XRD patterns of the alloy, with different additions of Y, show that the LAZ532 alloy is composed of -Mg and AlLi phases . With the
addition of Y, Al2Y peaks appear while AlLi peaks disappear gradually. Line scanning analysis for the polygonal compound in the alloy
shows that Al and Y contents increase quickly in the location of polygonal compound. EDS microanalysis indicates that the Al/Y ratio of
this compound is about 2:1. From these results, we conclude that the polygonal compound distributing inside grains is Al2Y
Result: Effect of Y on mechanical properties

the ultimate tensile strength and elongation to failure of the alloy with different Y contents. The tensile strength and elongation both
decrease to the lowest values when Y content is 0.4 wt.%. However, the tensile strength and elongation are improved significantly with
Y addition up to 0.8 wt.% where tensile strength reaches a peak value and increases by 32.66% compared with that of the alloy without
Y. Further increasing Y content results in the reduction of tensile strength, whereas elongation still improves and reaches a peak value
which increases by 15.6% compared with that of alloy without Y, when Y content is 1.2 wt.% However, both tensile strength and
elongation declined with 2.0 wt.% Y content. These results indicate that an appropriate addition of Y (about 1 wt.%) is effective for
improving tensile strength and ductility of the LAZ532 alloy.
6.Effect of Boron on the Grain Refinement and Mechanical Properties of as-Cast
Mg Alloy AM50
Introduction: Mg alloys are widely used to make components in numerous industries, such as aerospace, automobile, and
3C due to their low density, high specific strength and stiffness, good damping characteristics, electromagnetic shielding capacity,
adequate formability, and good cast ability. Grain refinement improves strength and ductility simultaneously . Grain refinement of
as-cast Mg alloy is achieved by alloying, and as a result of constitutional under-cooling. Grain refiners for Mg alloys are generally
divided into two types, classified by whether or not the Mg alloy contains Zr. Carbon inoculation is reported to be an effective
method of refining Mg–Al alloys because of its practical advantages such as low operating temperature, large melt volume, and
less fading with long holding times.

METHODOLOGY AND MATERIALS:

The AM50 alloy was prepared by melting commercially available pure Mg (99.9%), Al (99.9 %), and Mg–5Mn (95 wt. % Mg and 5wt.
% Mn) in a steel crucible an electrical resistance furnace (Experimental electric furnace factory, Shanghai, China) under a
protecting gas, which consisted of 99% CO2 and 1% SF6. The resistance furnace was heated to 670 ◦C, and pure Mg was put into
the crucible to be melted, then Al and Mg–5Mn was added to the Mg melt and then different amounts of the Al–3B master alloy was
added into the melt at a temperature of around 730 ◦C. The melt was continuously stirred for 10 min, held for 15 min, and poured
into a steel cylindrical mold, which was preheated to 300 ◦C. The casting was cooled in air and removed from the mold.
Microstructures were revealed using optical microscopy (OM) with a Zeiss Axio Observer A1 after polishing and etching with an
acetic picral solution containing 3 ml acetic acid, 3 g picric acid, 45 mL ethanol, and 5 mL distilled water. The grain size was
calculated by the intercept length method (IL, each grain size was calculated from around 100 counts), which measures the
distance between two adjacent grain boundary intersection points on a test line segment. The grain morphologies were observed
using scanning electron microscopy (SEM) after polishing and etching the sample with 4% nitric acid in alcohol.
RESULTS AND CONCLUSION:
These two phases were also identified in the typical SEM micrograph. show a
blocky particle, with a size of ~10 µm, identified as AlB2. A similar shape of a
typical particle in the Al–4B master alloy was also identified as AlB2 . The back
scattered electron (BSE) mode in Figure 2b gives a contrast better than in
Figure 2a between Al and AlB2, because AlB2 has a lower average relative
atomic number than Al. The particle was identified as AlB2 by EPMA from the
point analysis presented in Figure 2c,d of the particle marked with a red
cross.The influence of B addition on the microstructure and mechanical
properties of as-cast AM50 alloy was revealed in the present work. The major
conclusions are as follows: (i) The microstructure of as-cast AM50 alloy mainly
consists of Mg17A112, Al4Mn, and α–Mg phases. The microstructure did not
change significantly with the increasing B content. (ii) Boron is an effective and
cheap grain refiner for Al containing magnesium alloys, which is very important
for the die cast AM50 magnesium alloy parts. Alloying AM50 with 0.15 wt.% B
using the Al–3B master alloy refined the grain size from 550 µm to 100 µm; and
the ultimate tensile strength and the elongation increased by 37% and 33%. (iii)
The grain refiner was identified as MgB2 particles instead of AlB2, which were
located near the Al–Mn phase in the center of the grain. However, the MgB2
particle is not yet identified by TEM in this study, which will be further
investigated in the future
Link: https://doi.org/10.3390/ma12071100