Muhammad Rizqi Ramadhan

2715100116

Boron in Steel
The Basic Properties of Boron

The name "boron" originates from the Armenian-Persian linguistic area: buraq or burah for
borax, one of the most widely-known boron compounds, namely sodium sodium
tetraboratedecahydrate. As long ago as the Middle Ages borax was exported under the name
"Tincal" from the salt lakes of Central Asia to Europe, where it was used as an aid in soldering
and melting.

The proportion of boron in the earths outer crust is estimated to be to 10ppm and in nature
boron does not occur in the elementary state, but always combined with oxygen. The
technically most important boron-containing minerals are:

Borax (Tincal): Na2O x 2B2O3 x 10H2O;

Tincalconite: Na2O x 2B2O3 x 5H2O;
Kernite (Rasorite): Na2O x 2B2O3 x 4H2O;
Boracite: 5MgO x MgCl2 x 7B2O3;
Colemanite: 2CaO x 3B2O3 x 5H2O;
Sassolin: B2O3 x 3H2O.

The greatest deposits of boron are located in Kazakhstan, California, Argentina and Turkey.
Boron was first successfully produced in 1808 by H. Davy, as amorphous. Boron is the only
nonmetal of the third main group of the periodic table. At the atmospheric pressure and
temperature of 0C boron is a solid material. It has six isotopes, some of which are radioactive
with very short time of semi decay, below 1 second. Some of the most important properties of
boron are listed in the tables 1, 2 and 3.

Modification Amorphous Crystaline

Color Brown Black-grey
Phase
Temperature of occurrence, C 800-1100 1300 1100-1300
Lattice type rhombohedral tetragonal
a=1,789 nm
b=0,895 nm
c=1,015 nm

Table 1: Boron: structural data

Amorphous Crystaline
mod. 2.46
Density, g/cm 1.73 mod. 2.35
mod. 2.37
Hardness 9.3
amorphous 1.6-2.4
Tensile strength, MPa
fibres 2.6-3.1
 Compressive strength, MPa 0.5
Elasticity modul, MPa 440

Table 2: Boron: mechanical properties

Flame point, C 70
Melting point, C 2300
Boiling point, C 2550
Coefficient of thermal expansion 20-750 1.1- 8.3 nm/m.k
Latent heat of vaporization 34900 kg/kg
Latent heat of fusion 22000 kJ/kg
Latent heat of combustion 5.4 kJ/kg
D= 0.002 e-21000RT
Diffusion coefficient in -Fe
for t=1000 C : D=0.002

Table 3: Boron: thermodynamic data

According to P.E. Brushby et al. boron diffusion velocity is the same as carbon diffusion
velocity (diffusion coefficient D=0,002e-21000/RT). With carbon content of up to 0.43%, the
solubility of boron in the austenite lattice is independent of the carbon content. Carbon
diffusion is not affected up to boron contents of 0,009%.

Boron Solubility in Pure Iron

There are different opinions about the positions of boron atoms in the iron crystal lattice. Based
on comparison of the diffusion coefficients of carbon and boron, Jandeska and I.J.Morral have
concluded that the boron atoms are interstitially dissolved in the -Fe lattice. C.C. McBride,
J.W. Spretnak, R.Speiser have reached the same results based on comparison of the theoretical
consideration of the boron atoms radius and interatomic distances in the -Fe lattice. However,
these geometric considerations ignore the mechanisms of physical and chemical bonding.

R.M.Goldhoff and J.W.Spretnak found by X-ray deflection measurements that the lattice
parameter in gamma iron is reduced in the presence of boron. They took this as a proof of a
substitutional dissolution of the boron atoms in the austenite lattice. Due to the atomic radii of
boron and iron, they considered the position of the boron atoms at the lattice locations to be
more favorable than at intermediate lattice locations.

They also discovered that the difference between the lattice parameters of pure iron and boron-
containing iron decreases with increasing temperature. From this they concluded that with
increasing temperature more boron atoms migrate from the lattice to the grain boundaries,
where boron separations have actually been found. However, these authors did not exclude the
possibility that a smaller number of boron atoms may also occupy intermediate lattice
locations.

There is several different works on the Fe-B binary system. Figure 1 shows a diagram prepared
by O.Kubaschevsky. It shows two eutectics, one at 17 atomic percent of boron, the other at
63.5% of boron.
 Figure 1: Kubaschewsky Fe-B phase diagram

Within the range between these two eutectics, the liquidus temperature varies between 1149C,
the eutectic temperature at 17 atomic percent of boron, and 1590C for the alloy with 50 atomic
percent of boron. Accordingly, the melting temperature of iron can be lowered by more than
150C to the maximum of 350C (at 17 atomic percent of boron) by the adding of 5 to 30
atomic percent of bor. By increasing proportion of boron in the ferroboron from the second
eutectic, the liquidus temperature rises steadily and almost linearly up to the melting
temperature of pure boron. Accordingly, in the above diagram, iron boride (FeB) has 16.23
weight percent of boron, a rhombic lattice and extreme hardness of 2300 HV0.2

Iron-II-boride (Fe2B) has 8.83 weight percent of boron, a tetragonal lattice and hardness of
1800 to 2000 HV0.2 (preferable as long as FeB is being avoided). Many authors have made
more precise investigations of the iron/boron binary system in the iron rich corner. According
to Houndremon's binary phase diagram Fe-B (Figure 2), in the low concentration region of
boron the maximum solubility of boron is 0,021% at 1149C. In the meantime, with the
temperature decrease its solubility decreases too, as far as down to 0.0021% at 906C.

At the same time this temperature is perytectoide for perytectoide reaction at 0.0082%B. Boron
solubility in -Fe suddenly decreases and at 710C only about 0.0004% of boron substitionally
dissolved.
 Figure 2: Equilibrium phase Fe-B diagram for low boron concentrations

J.W.Spretnak investigated whether it is possible for boron to form a film surrounding austenitic
grain in the steel and concluded on the basis of the geometrical considerations that it is
impossible. Instead, they discovered a point Fe2B precipitation at the grain boundaries. In the
steel, boron can be dispersed in matrix in the form of Fe2B, boride with size of 20 to 30x10-8
cm and free, which segregates predominantly surrounding primary austenite grain boundaries.
This small amount of the soluble boron arranged along grain boundaries, evidently retards -
transformations by diffusion, namely it prevents feritic reaction thus enhancing hardenability
of the steel.

Boron optimum quantity which has to be added in the steel to achieve maximum hardenability,
based on experience is about 0.0003 to 0.0030% B. Boron addition beyond the mentioned
values deteriorates hardenability because the excess of boron atoms precipitates as the surface
centered cube Fe23(CB)6 borocarbide which can be a ferrite nucleation preferential place.

Available Forms

Boron is supplied to steelmakers as ferroboron or as one of several proprietary alloys. Choice

of addition depends, as always, on steelmaking practice, product mix and volume, individual
operators' experience and preference, and price. A steelmaker should choose that addition agent
giving the highest and most reliable recovery consistent with his overall melt shop economics.

Ferroboron is the lowest cost addition agent. Boron content is relatively high: standard grades
are sold with incremental boron levels between 12 and 24% B. Major impurities are carbon
(0.10-1.5%), silicon (0.30-4.0%) and aluminum (0.5-8.0%). A typical analysis will include
18.0% B, 0.50% C, 0.50% Si, 0.2% Al, 0.03% P, and 0.01% S. All except boron are maximum
values. Product is supplied in lump form, 2 in. or 1 in. x down, packaged in 250 kg or 500 lb
steel drums, or supersacks (bulk bags) of up to 3000 lb (1360 kg) capacity. Many customers
apply a minimum size limit, such as 5 mm (0.2 in.), in order to minimize the amount of fine
material, which can give poor recoveries in less well-controlled melting practices. Ferroboron
is also available as cored wire.

Because ferroboron does not contain appreciable concentrations of protective elements, it

requires greater care than the proprietary alloys in order to give adequate and consistent results.
It is normally added after other oxygen/nitrogen scavengers, such as ferrotitanium.

The proprietary boron addition agents are more expensive than ferroboron on an initial cost
basis but are often preferred for their greater efficiency, ease of application and more consistent
results. All will contain varying proportions of oxygen and/or nitrogen scavengers such as
titanium, aluminum, silicon and zirconium. These elements generally have an even greater
affinity for oxygen and nitrogen than boron.

The most common proprietary addition agent typically contains 2.0% B, 15% Al, 30% Ti, 10%
Si, bal. Fe. This product's high scavenger/boron ratio ensures its effectiveness for all boron
steels, provided they have been adequately deoxidized first.

A variety of other composition proprietary boron addition alloys are available, with boron
contents varying between 0.5% and 4%. Generally, the higher the ratio of boron to scavenger
elements, the greater the care required to ensure adequate recovery of the boron in the steel.

Proprietary boron addition agents are sold in lump form 1-1/4 in. and 2 in. x down, packaged
in bags, cans or large drums.

Boron in steel as an alloying element

Boron is useful as an alloying element in many materials, but here it will be illustrated as an
alloying element in the steel because of its effect on hardenability enhancement. Boron is added
to unalloyed and low alloyed steels to enhance the hardness level through enhancement
hardenability. Boron added to high-speed-cut steels, for example, containing 18%W, 4%Cr
and 1%V, enhances their cutting performance, but reduces their forging qualities.

Addition of boron in a quantity of up to 0.01% to austenitic steels also improves their high-
temperature strength. Boron steels are used as high-quality, heat-treatable constructional steels,
steels for carburization and cold forming steels such as steels for screws. The addition of 5 to
50 ppm B to ferritic steels containing 14 to 18% Cr may improve the surface quality of stainless
strips by avoiding errors, such as scale, ribbing a roping, and ridging, which otherwise
frequently occur in strip production.

The basic effect of boron on in the steel is the enhancement of hardenability, which is evident
already at a very small concentration, of the degree of 0.0010% of boron. It is added to
unalloyed and low alloyed steels for the hardness level enhancement through the hardenability.
Even in the small quantity of the degree of size up to 100 ppm, boron gives the same effect of
the hardenability enhancement as other more expensive elements which must be added in much
bigger quantity. For example the addition of 30 ppm B in SAE replaces approximately 1%Ni,
0,5%C, 0,2%Mn, 0,12%V, 0,3%Mo or 0,4%Cr.
The Figure 1 shows hardenability curves of the boron low alloyed steels (13MnCrB5)
compared to the steel without boron (16MnCr5).

An addition of 30 ppm of boron in steel which contains approximately 0.15%C, 1%Mn and
0.9%Cr shows a clear increase in hardness of almost 50% to a larger depth from the surface
than in the case of a steel of identical composition, but free from boron (see Figure 1).
According the same authors, there is no difference in hardness on the surface between the
boron-containing and the boron-free steel, which can be seen in the Figure 1, too. Accordingly,
the incipient hardness is therefore determined not by boron, but by the martensitic structural
state influenced by the carbon content. The hardness-enhancing effect of boron comes into play
only below the surface.

The mechanism which is decisive for the enhancement of hardenability by boron is a delay in
the transformation to the bainite, ferrite and pearlite structures, which are softer than
martensite. Unless prevented by boron, these softer structures would be formed during the
cooling from the austenitisation temperature, after annealing or hot working.

Figure 1: Boron effected hardenability of steel

The Boron hardenability effect

An outstanding feature of boron steels is the improvement in hardenability produced by the

addition of even a minute quantity of boron. It is generally accepted that a hardenability peak
is reached when the quantity of boron is between 3 and 15 ppm. In an excessive amount of
boron (>30 ppm) is present, the boron constituents become segregated in the austenite grain
boundaries, which not only lowers hardenability, but also may decrease toughness, cause
embrittlement and produce hot shortness. The affect of boron on hardenability also depends on
the amount of carbon in the steel. The effect of boron increases in inverse proportion to the
percentage of carbon present.

Boron must be in its atomic state to improve hardenability, which means that care must be
taken during steel production for the boron to be effective. Boron may also become ineffective
if its state is changed by incorrect heat treatment. For example, high austenitizing temperatures
must be avoided as well as temperature ranges where certain boron precipitates occur.

Hardenability is highly dependent on the behavior of oxygen, carbon and nitrogen present in
steel. Boron reacts with oxygen to form boron oxide (B2O3); with carbon to form iron
boroncementite (Fe3(CB)) and iron boroncarbide (Fe23(CB)6); and with nitrogen to form boron
nitride (BN). Loss of boron by oxygen is presented by making the boron addition to silicon-
aluminum killed steels and by using good ladle and mold practices. Strong nitride formers
(titanium, aluminum, and zirconium) protect the boron from reaction with nitrogen. For
example, if nitrogen is fixed by using titanium, satisfactory hardenability is obtained in the
temperature range up to 1830F (1000C) provided that the steel contains about 5-20 ppm of
boron.

The hardenability of boron steel is also closely related to austenitizing conditions and is
generally said to decrease by heating above 1830F (1000C). Boron steel must also be
tempered at a lower temperature than other alloy element steels of the same hardenability.

Applications

Boron steels are used for a variety of applications, as a wear material and as a high strength
structural steel. Examples include punching tools, spades, and knives, saw blades, safety beams
in vehicles etc.

Carbon-manganese-boron steels are generally specified as replacements for alloy steels for
reasons of cost: C-Mn-B steels are far less expensive than alloy steels of equivalent
hardenability. Applications for these steels include earth scraper segments, track links, rollers,
drive sprockets, axle components and crankshafts.

Boron alloy steels are specified when the base composition meets mechanical property
requirements (toughness, wear resistance, etc.), but hardenability is insufficient for the intended
section size. Rather than call for a more highly alloyed and therefore more expensive steel, a
user may simply specify the corresponding boron grade, thereby ensuring suitable
hardenability.

An expanding area of boron usage is the field of high strength low alloy (HSLA) and other
structural steels. These may be supplied as hot rolled or as quenched and tempered (for boron
grades, the latter are more common). Boron assures adequate hardenability in heavier plate
sections.

Boron is sometimes used in non-heat treated steels. Ferroboron may be added as an intentional
nitrogen scavenger in carbon steels for automotive strip stock. By avoiding interstitial nitrogen,
boron makes the steel more formable. Aluminum is sometimes used for a similar duty, but AlN
is slower to precipitate, so requiring higher annealing temperatures. Boron addition makes the
steel more formable and eliminates the need for strain age suppressing anneals.
Boron has a high neutron absorption capability. For this reason, it is added to certain types of
stainless steel for use in the nuclear industry. Levels of 4% boron or more have been used, but
the lack of hot ductility and weldability mean that boron contents of 0.5 to 1.0% are more
common for neutron absorption application. Nonetheless, even at these boron contents, the
ferroboron has to be of the highest purity.

This range of medium carbon steels with a deliberate boron addition improves hardness during
heat treatment (Boron 922, C=0.25-0.30% and Boron 921, C=0.38-0.42%). Toughened by
tempering following oil or water quenching, boron steels possess a hardness equivalent to that
of much higher carbon steels and of more expensive low alloy steels. Advantages of boron
steels are; improved cold formability, lower delivered hardness giving improved blanking tool
life, improved weldability due to low carbon equivalents, lower tempering temperatures giving
savings on energy, and good case hardening response. Typical applications include toecaps and
chains.

The type of boron steel used on vehicles today has extremely high strength. The boron steel
used on Volvo cars has a yield point of about 1,350-1,400 MPa (196,000-203,000 psi). Thats
about four times stronger than average high-strength steel. But the process used to make it that
strong takes away some of the steels workability properties, such as being able to straighten
it.

For now, boron steel is found primarily on European vehicles, such as the dash panel on the
2002 Porsche Cayenne SUV, the safety bar around the rear seats on the 2003 Porsche Boxster,
the door guard beams on the 2003 Porsche 911 Carrera, and the inner B-pillars on the 2003
Mercedes-Benz E Class. Volvo probably uses boron steel the most. Boron is used on the
bumper reinforcements and guard beams on the 2004 Volvo S40 sedan and 2005 V50 station
wagon. The 2003 Volvo XC90 SUV has several applications of boron steel, including the inner
B-pillar reinforcements, the roof bow between the B-pillars (if there is no sunroof), and the
inner rear body panels. The 1999-2004 S80 and 2001-2004 V70 and S60 also have boron steel
inner and outer rear body panels.