Effects of Alloying Elements in Steel

Steel is basically iron alloyed to carbon with certain additional elements to give the required
properties to the finished melt. Listed below is a summary of the effects various alloying
elements in steel.

 Carbon
 Manganese
 Chromium
 Nickel
 Molybdenum
 Titanium
 Phosphorus
 Sulphur
 Selenium
 Niobium
 Nitrogen
 Silicon
 Cobalt
 Tantalum
 Copper

Carbon
The basic metal, iron, is alloyed with carbon to make steel and has the effect of increasing the
hardness and strength by heat treatment but the addition of carbon enables a wide range of
hardness and strength.

Manganese
Manganese is added to steel to improve hot working properties and increase strength, toughness
and hardenability. Manganese, like nickel, is an austenite forming element and has been used as
a substitute for nickel in the A.I.S.I 200 Series of Austenitic stainless steels (e.g. A.I.S.I 202 as a
substitute for A.I.S.I 304)

Chromium
Chromium is added to the steel to increase resistance to oxidation. This resistance increases as
more chromium is added. 'Stainless Steel' has approximately 11% chromium and a very marked
degree of general corrosion resistance when compared with steels with a lower percentage of
chromium. When added to low alloy steels, chromium can increase the response to heat
treatment, thus improving hardenability and strength.
Nickel
Nickel is added in large amounts, over about 8%, to high chromium stainless steel to form the
most important class of corrosion and heat resistant steels. These are the austenitic stainless
steels, typified by 18-8, where the tendency of nickel to form austenite is responsible for a great
toughness and high strength at both high and low temperatures. Nickel also improves resistance
to oxidation and corrosion. It increases toughness at low temperatures when added in smaller
amounts to alloy steels.

Molybdenum
Molybdenum, when added to chromium-nickel austenitic steels, improves resistance to pitting
corrosion especially by chlorides and sulphur chemicals. When added to low alloy steels,
molybdenum improves high temperature strengths and hardness. When added to chromium steels
it greatly diminishes the tendency of steels to decay in service or in heat treatment.

Titanium
The main use of titanium as an alloying element in steel is for carbide stabilisation. It combines
with carbon to for titanium carbides, which are quite stable and hard to dissolve in steel, this
tends to minimise the occurrence of inter-granular corrosion, as with A.I.S.I 321, when adding
approximately 0.25%/0.60% titanium, the carbon combines with the titanium in preference to
chromium, preventing a tie-up of corrosion resisting chromium as inter-granular carbides and the
accompanying loss of corrosion resistance at the grain boundaries.

Phosphorus
Phosphorus is usually added with sulphur to improve machinability in low alloy steels,
phosphorus, in small amounts, aids strength and corrosion resistance. Experimental work shows
that phosphorus present in austenitic stainless steels increases strength. Phosphorus additions are
known to increase the tendency to cracking during welding.

Sulphur
When added in small amounts sulphur improves machinability but does not cause hot shortness.
Hot shortness is reduced by the addition of manganese, which combines with the sulphur to form
manganese sulphide. As manganese sulphide has a higher melting point than iron sulphide,
which would form if manganese were not present, the weak spots at the grain boundaries are
greatly reduced during hot working.

Selenium
Selenium is added to improve machinability.
Niobium (Columbium)
Niobium is added to steel in order to stabilise carbon, and as such performs in the same way as
described for titanium. Niobium also has the effect of strengthening steels and alloys for high
temperature service.

Nitrogen
Nitrogen has the effect of increasing the austenitic stability of stainless steels and is, as in the
case of nickel, an austenite forming element. Yield strength is greatly improved when nitrogen is
added to austenitic stainless steels.

Silicon
Silicon is used as a deoxidising (killing) agent in the melting of steel, as a result, most steels
contain a small percentage of silicon. Silicon contributes to hardening of the ferritic phase in
steels and for this reason silicon killed steels are somewhat harder and stiffer than aluminium
killed steels.

Cobalt
Cobalt becomes highly radioactive when exposed to the intense radiation of nuclear reactors, and
as a result, any stainless steel that is in nuclear service will have a cobalt restriction, usually
aproximately 0.2% maximum. This problem is emphasised because there is residual cobalt
content in the nickel used in producing these steels.

Tantalum
Chemically similar to niobium and has similar effects.

Copper
Copper is normally present in stainless steels as a residual element. However it is added to a few
alloys to produce precipitation hardening properties.
 Abstract:
Phosphorus in steel can have beneficial as well as harmful effects. Phosphorus is one of
the most potent solid-solution strengtheners of ferrite. The addition of only 0.17%
phosphorus increases both the yield and tensile strength of low-carbon sheet steel by
about 62 MPa (9 ksi) while also improving the bake hardening response and deep
drawability. Because of these properties, rephosphorized high-strength steels are widely
used for cold-forming applications. Phosphorus is also used as an additive in steels to
improve machining characteristics and atmospheric corrosion resistance.

Phosphorus in steel can have beneficial as well as harmful effects. Phosphorus is one of the most potent solid-
solution strengtheners of ferrite. The addition of only 0.17% phosphorus increases both the yield and tensile strength
of low-carbon sheet steel by about 62 MPa (9 ksi) while also improving the bake hardening response and deep
drawability. Because of these properties, rephosphorized high-strength steels are widely used for cold-forming
applications. Phosphorus is also used as an additive in steels to improve machining characteristics and atmospheric
corrosion resistance.
Detrimental effects of phosphorus in steel include various forms of embrittlement which reduce the toughness and
ductility. The most familiar example in this category is the classic phenomenon of temper embrittlement in heat-
treated low-alloy steels resulting from segregation of phosphorus and other impurities at prior austenite grain
boundaries. This form of embrittlement and the contributing role of certain alloying elements has been a subject of
research for several decades.
Two other forms of intergranular embrittlement can occur in steels containing phosphorus in the normal range of
0.008 to 0.025%. In both types, fracture follows the ferrite grain boundaries (instead of prior austenite grain
boundaries) weakened by the segregation of phosphorus during slow cooling of coiled strip or during final annealing
after cold rolling. In one type, planar-oriented cracking (separation) is observed in the production of high-strength,
low-alloy strip for line pipe. In the other type, brittle fracture may occur during secondary cold working of sheet steel
that has previously been deep drawn (with elongated ferrite grains creating planes of relative weakness) or during
service of the drawn part. As most texts on metallurgy emphasize, phosphorus also increases the hardenability of
steel.
Several studies have demonstrated that although the magnitudes of the effects observed vary considerably. The
most common method for calculating hardenability from steel composition as outlined in standards ASTM A255 and
SAE J406 does not consider the effect of phosphorus. The explanation for this omission is that the effects of
phosphorus and sulfur in residual amounts tend to cancel one another. Because of its detrimental effects on
toughness and ductility of heat-treated steels, phosphorus addition is generally not employed for increasing
hardenability. Table 1 summarizes the effect of phosphorus on the properties of various grades of steel.
Table 1: Summary of the effects of phosphorus on the properties of various steel grades.
PROPERTY EFFECT
Strength Strong increase
Bake hardenabillity Increase
Ductility Strong decrease
Texture (R-value) Depends on composition and processing
Coating behavior:  
Fe-Zn Galvanneal Demands control of phosphorus. Can improve powdering.
Phosphatability May improve
Enameling steels Improves fishscaling. Accelerates pickling.
Spot weldability Not harmful up to ~0.1%
Core loss of motor lamination steel Strong decrease (improvement)
Embrittlement Aggravates
Very low Phosphorus
The P requirement for this category ranges up to about 0.02%. Steels with very low maximum phosphorus
requirements include those that are particularly susceptible to embrittlement. These are mainly high-strength, low-
alloy steels containing, for example: Mn, Si, Ti, Nb, V, Mo, Cr, etc.
While most attention seems to have been focused on residual sulfur reduction, the trend now is to reduce the levels
of all residuals including phosphorus. Line pipe steels are among the most demanding as regards low phosphorus
content. For the transmission of corrosive gases maximum content of phosphorus P=max 0.02% will be necessary
and P=max 0.01% is desirable. The phosphorus content less than 0.01% will be indispensable for low temperature
service.
Demand for higher formability has increased the use of stabilized, ultra-low carbon steels. As mentioned previously,
these steels are susceptible to secondary-work embrittlement in deeply drawn parts. Although boron additions
alleviate this problem, boron exerts a negative impact on formability, Lower phosphorus levels, below 0.01 percent,
represent a potential alternative solution to the secondary work embrittlement problem.
Moderately Low Phosphorus
Products for which roughly 0.02% to 0.03% phosphorus is tolerable include most low-strength grades and high-
strength steels that are not subject to hostile environments. Whenever high ductility is required, phosphorus should
be kept as low as possible, while keeping in mind the increased cost of reducing the phosphorus level.
For commercial quality, plain-carbon steels where formability requirements are minimal, the upper limit of range can
be somewhat relaxed. From a product consistency standpoint, tight control of phosphorus is more important than
reducing its level below about 0.02% for steels that fall into this category.
High Phosphorus (Rephosphorized)
Phosphorus is commonly used as a strengthening agent in amounts up to about 0.1%. Also, as much as 0.155% P
is added to cold rolled, motor lamination steels to reduce AC core loss.
As discussed previously, many properties are sensitive to the phosphorus content and the effect of phosphorus
depends on the processing method. In addition, processes such as galvanneling are sensitive to the phosphorus
content of the base steel. Therefore, tight control of the phosphorus level and choosing the proper process route are
important if consistent properties are to be obtained and embrittlement problems avoided.
Strength
Phosphorus is one of the most potent solid solution strengtheners of ferrite. Hence, small additions of phosphorus
are used to inexpensively increase the strength of low carbon sheet steel. Figure 1 compares the change in lower
yield strength of carbon steel as a function of alloy addition for several common elements.
Among the elements considered, only carbon and nitrogen produce a greater strengthening effect than phosphorus.
This is related to the fact that phosphorus enters the crystal lattice as a substitution solute, whereas carbon and
nitrogen are interstitial solutes in ferrite. Nevertheless, the addition of only 0.1 wt. % of phosphorus raises the yield
strength by about 62 MPa (9 ksi). A similar effect of phosphorus is observed on ultimate tensile strength. In addition,
the strengthening effect of phosphorus does not appear to be sensitive to the carbon content of the steel.
 Figure 1: Change in the lower yield strength of carbon steel as a function of the alloy content for several common
elements (1ton/inch2 = 13.8 MPa)
The effect of grain size on strength is influenced by the phosphorus content in ferrite. By additions of up to about 0.1
percent of phosphorus, particularly in the case of ultra-low carbon ULC steels with C=max 50 ppm.
Cold working increases the strength of most metals through the process of work hardening (strain hardening). For an
annealed metal, work hardening has a stabilizing influence on plastic deformation which delays fracture and
enhances ductility. Thus, a high capacity for work hardening is important for products that require high formability.
Phosphorus has a tendency to reduce the work-hardening rate of ferrite. But only a minor decrease in the strain-
hardening exponent, n, with increasing phosphorus up to 0.12 percent was observed by Hu in laboratory processed
low carbon, Al-killed steel. The detrimental effect of P on n is greater in Ti-stabilized ULC steel. But the n-value of
this steel still maintained high levels, in excess of 0.27 even at 0.1 percent of phosphorus. Thus it appears that the
work-hardening capacity of ferrite is not seriously impaired by dilute additions of phosphorus.
Bake Hardening
With proper control of steel composition and processing, an increment in hardening can be induced by heating
certain steels after plastic straining. This effect, known as bake hardening, can be economically exploited during the
plant-bake cycle of formed sheet steel parts in which the peak steel temperature reaches approximately 170°C.
Bake hardening is associated with carbon and/or nitrogen strain aging whereby mobile dislocations are pinned by
interstitial atoms pr clusters. Hence, the magnitude of the bake-hardening effect depends on the amount of carbon
and/or nitrogen retained in solid solution after final processing. In addition, strain aging (and bake hardening)
depends on grain size-the effect increase with decreasing grin size.
The effect of phosphorus on bake hardening in carbon steels has received considerable attention. It is generally
agreed that phosphorus enhances bake hardening in low-carbon steels, Al-killed steels, although the effect probably
applies to other steels as well. Figure 2 demonstrates this effect in low carbon 0.04%C Al-killed steel, where bake
hardening represents the increase in yield strength for a tensile specimen strained 2 percent and heated for 20
minutes at 170°C.
Hanai et al. attributed the increase in bake hardening by phosphorus to grain refinement during annealing. The steel
with 0.06%P exhibited a ferrite grain size one order of magnitude finer than similar steel with 0.01%P given similar
processing treatments. Furthermore, phosphorus had a negligible effect on the solute carbon a nitrogen contents
remaining in solution after processing. Therefore, grain refinement by phosphorus was cited as the cause of
increased bake hardening.

Figure 2: Effect of phosphorus content on the bake hardening increment in 0.04 Al-killed steels (1kg/mm2 = 9.8
MPa)
Ductility
As expected, the strengthening effect of phosphorus is accompanied by a concomitant decrease in ductility. For
example, Figure 3 shows the relationship between the decrease in elongation and increase in tensile strength
resulting from P, Mn and Si additions to a Ti-stabilized, ULC steel. Thus, phosphorus (and other strengthening
elements) decreases formability so that a balance between strength and formability must be considered in designing
high strength formable steels. At high phosphorus levels (depending on composition, processing, etc.) ductility is
severely limited by embrittlement phenomena associated with phosphorus segregation to grain boundaries.
 Figure 3: Decrease in ductility (percent total elongation) with tensile strength for P, Si and Mn-strengthened Ti-
stabilized, ultra low carbon steels

Anisotropy of plastic-flow properties has a strong influence on the deep drawability of sheet steels. For good
drawability the through-thickness strength in order to avoid thinning during drawing operations. A useful measure of
drawability is the R-value, defined as the ratio of width to thickness strain in a uniaxial tensile specimen at fixed
extension (typically 17 percent). Since the R-value generally varies with direction in the sheet, a mean R-value is
typically reported. A high R-value implies good drawability with values of 2.0 being considered excellent.
Plastic anisotropy is determined by crystallographic texture i.e. the orientation distribution of grains within the sheet,
which is closely related to steel composition and processing. In body centered cubic materials (e.g. carbon steels)
favorable drawing textures correspond to a high proportion of {1 1 1} planes aligned parallel to the sheet surface. The
topic of annealing textures in steels has been thoroughly reviewed by Hutchinson.
Phosphorus affects the texture and R-value of cold rolled steel in a complex manner that is dependent on the
composition of the steel and the annealing treatment. Early investigations showed that up to 0.04 percent of
phosphorus markedly improves the R-value of low-carbon rimmed steel given a decarburizing open-coil anneal. Hu
also noted an improvement in the R-value from about 1,5 to 2,0 with the phosphorus content ranging from
%P=0,004÷0,12 in vacuum-melted rimmed steels given a simulated batch anneal.
However, Al-killed steels that were air melted showed a less dramatic improvements in the R-value which appeared
to reach a maximum at about %P=0.08. Hu proposed that segregation of phosphorus to grain boundaries and
subgrain boundaries influences the nucleation and growth of recrystallized grains. He showed that the recrystallized
texture is significantly altered by phosphorus additions to Al-killed steel.
More recent work has demonstrated the importance of the heating rate during annealing, carbide morphology and
solute carbon content. Ono et al. showed that both low phosphorus (%P=0.016) cold rolled, low carbon, Al-killed
steels exhibit a maximum in R value versus heating rate during annealing. At an optimum heating rate of about
50°C/hour, the high phosphorus steel had a lower R value than the low phosphorus steel, whereas the opposite was
observed at heating rates greater than 80°C/hour. These effects were attributed to an interaction between P and AlN
precipitation during annealing, which in turn, affected the final grain structure and crystallographic texture.
In a subsequent paper, these authors describe an experiment whereby interference from AlN was eliminated by heat
treatment prior to cold rolling. Treatments were varied such that a decarburized steel (20-30 ppm C) and steels with
fine and coarse Fe-carbide precipitates were produced. Figure 1 summarizes the results of annealing experiments for
these steels.

Figure 1: Effect of the heating rate on the R-value as a function of the phosphorus content and carbide morphology
in Al-killed steels. ALN precipitation was complete prior to cold rolling and annealing.
For the decarburized steel, the R-value decreased with both increasing P content and faster heating rate during
annealing. This apparently reflects the behavior of ultra-low-carbon, carbide-free matrix. At low heating rates
phosphorus improved the R-value for both coarse- and fine-carbide steels. This may indicate that phosphorus
reduces the inhibiting effect of carbon which enters solution via carbide dissolution prior to recrystallization. At high
heating rates phosphorus degraded the R-value of coarse-carbide steel. In the fine-carbide steel, the R-value first
increased slightly and then decreased with increasing P content. This suggests that either phosphorus had
insufficient time to segregate to grain or subgrain boundaries or that carbide dissolution had not progressed
sufficiently to show a beneficial effect of phosphorus.
Hutchinson concluded that phosphorus is only beneficial in those situations where dissolved carbon would otherwise
degrade texture. Furthermore, in order to be effective, phosphorus must be allowed to segregate e.g. during slow
heating. However, in the case of Ti stabilized, ULC steels where virtually carbon does not exist in solution during
annealing, small phosphorus additions tend to improve the R-value. Figure 2 shows this effect as a function of grain
size for samples rapidly heated to 800°C. Note that at the same time grain size, the R-value of the P-bearing steel is
up to 0.3 units greater than that of the base steel. Further study is needed to elucidate the effect of phosphorus on
texture development in stabilized steels.

Figure 2: R-value as a function of grain size for rapidly annealed, Ti-stabilized, ultra-low carbon steels containing Si,
Mn or P.
Although the available data is somewhat confusing, up to 0.1 percent of phosphorus does not appear to seriously
impair the drawability (R-value) of carbon steels. Furthermore, with the proper choice of processing parameters,
drawability can be significantly improved by additions of phosphorus; any improvement is usually a side benefit to the
strengthening effect of phosphorus, however. It is interesting to note that phosphorus is the only known element
capable of increasing both the strength and R-value of steel.
Spot Weldability
Sawhill and Baker compared the resistance spot-welding characteristics of plain-carbon steel with those of
rephosphorized steel containing 0.04 percent to 0.12 percent of phosphorus. Adequate weld button size, strength and
toughness were obtained over a practical range of welding conditions.
To obtain an adequate button size over a large range of weld currents, electrodeface diameters and welding times
need to be increased slightly compared with those of plain-carbon steels. Others report excellent weldability of
rephosphorized Al-killed steel and galvannealed Ti stabilized, ULC steel, although it has been suggested that the
phosphorus content be limited to approximately 0.1 percent.
Magnetic Properties (Core Loss)
Phosphorus is added in amounts up to 0.15 percent to cold rolled, motor-lamination steels in order to reduce AC core
loss during service. A significant portion of core loss is due to eddy currents, and this contribution depends inversely
on electrical resistivity. Phosphorus is desirable for this purpose because it strongly increases resistivity at low cost.
The enhanced punchability of motor laminations due to the hardening effect of P is an additional benefit gained by
adding phosphorus to these steels.
Coating Behavior
Phosphorus has a strong effect on the alloying rate of galvannealed Fe-Zn coatings in low-carbon, aluminum killed
steels. Phosphorus in the base steel retards alloy layer formation, thus reducing the alloying rate during
galvannealing. This is not necessarly detrimental since the galvanneling temperature can be increased to maintain
high productivity.
However, very soft steels may encounter shapes problems at galvanneling high temperatures. Nevertheless, tight
control of phosphorus is desirable in order to specify optimum operating conditions (temperature, line speed, etc.) for
a given steel grade. Variable phosphorus content can lead to difficulties in process control.
Phosphorus exerts a beneficial effect on the galvanneling reaction by inhibiting the so called "outburst reaction" at
grain boundaries which contributes to poor powdering performance. The outburst reaction refers to the formation of
brittle Fe-Zn intermetallic compound at ferrite grain boundaries. Volume expansion during this process causes the
grain boundary to open up, breaking a protective Fe-Al layer. This allows liquid Zn to locally form new intermetalics.
Phosphorus segregation to grain boundaries apparently inhibits the local Fe-Zn intermetallic formation.
Figure 3 shows results of investigation the effects of phosphorus in steels on the formation of Fe-Zn compounds in
continuously galvanized Nb-B-P-ultra low carbon steel sheets (%C=0.006; %Mn=0.27; %P=0.076; %S=0.005;
%Nb=0.016; %B=0.0018; %Alsol=0.004; %N=0.0023) which suggest that phosphorus inhibits the formation of outburst
structure.

Figure 3: The effects of phosphorus on formation of Fe-Zn compounds outburst structure.

Sheet steels coated with Zn or Al-Zn can become embrittled by heating in the temperature range of 335°C to 400°C.
This is a result of Zn penetration into the grain boundaries at temperatures less than the melting point of Zn.
Embrittlement can be prevented if the P content in the steel exceeds 0.04 percent. Phosphorus segregation to ferrite
grain boundaries inhibits intergranular diffusion of Zn, thus preventing Zn embrittlement.
Phosphatability was found to be markedly improved by the addition of 0.07 percent P to a Nb-bearing, ULC steel. In
addition, phosphorus markedly improved the corrosion resistance of phosphated steel. The addition of phosphorus to
certain enameling steel grades has been reported to enhance fishscaling resistance and after-fire strength.
Furthermore, phosphorus accelerates etching and nickel deposition rates during pre-enameling treatments. Although
these latter effects may be advantageous, process control difficulties can arise if the phosphorus content is not
consistently controlled to a predetermined level.