Iron Based Amorphous Alloys Using High Phosphorous Blast Furnace Grade Hot Metal
Abstract:
An iron-based amorphous alloy comprising: blast furnace hot metal 75-100 (wt %) and rest alloying elements 0-25 (wt %), the alloying elements comprising at least one or in combinations of phosphorus (P), niobium (Nb), chromium (Cr), molybdenum (Mo) and boron (B) and the blast furnace hot metal comprising Carbon (C)- 3.5-4.0, phosphorus (P)- 1.4-1.6, silicon (Si)- 2.00, manganese (Mn)-0.5-0.7, sulphur (S)-0.030 and rest iron (Fe), all in wt %.
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C/O. TATA STEEL LIMITED,
Research and Development and Scientific, Services Division, Jamshedpur-831001, Jharkhand, India
2. Pavan Bijalwan
C/O. TATA STEEL LIMITED,
Research and Development and Scientific, Services Division, Jamshedpur-831001, Jharkhand, India
3. Abhishek Pathak
C/O. TATA STEEL LIMITED,
Research and Development and Scientific, Services Division, Jamshedpur-831001, Jharkhand, India
4. Nilanjan Mahata
C/O., INDIAN INSTITUTE OF TECHNOLOGY KANPUR,
KANPUR, UTTAR PRADESH – 208016, INDIA
5. V.Venkatesh
C/O., INDIAN INSTITUTE OF TECHNOLOGY KANPUR,
KANPUR, UTTAR PRADESH – 208016, INDIA
6. Kallol Mondal
C/O., INDIAN INSTITUTE OF TECHNOLOGY KANPUR,
KANPUR, UTTAR PRADESH – 208016, INDIA
Specification
TITLE OF THE DISCLOSURE:
Iron based amorphous alloys using high phosphorous blast furnace grade hot metal
FIELD OF DISCLOSURE:
The present disclosurerelates to Fe based complete or partial amorphous alloy
compositions of varying glass forming abilities derived by suitable alloying with P, B,
Nb, Cr and Mo (either one or in combination) in blast furnace grade hot metal used as
base melt in varying quantities.
BACKGROUND OF THE DISCLOSURE
Since its first discovery of glass formation in metallic system Au-Si system by
rapid solidification in 1959 by P. Dowez[1] glassy alloys have gained huge attention for
their exciting combination of properties, like high strength, high stiffness, excellent
corrosion resistance, great soft magnetic properties in case of Fe-based alloys (like
“Finemet”). Over last 55 years of research have developed understanding on the
glassy alloys, both fundamentally as well as engineering application point of view.
These information can be seen in a number of excellent review articles [2].Fe-based
metallic glass constitutes one of the groups of the metallic glass family. Though Fe-
based glasses(like “Finemet”) possess excellent soft magnetic properties, some of the
multicomponent Fe-based glasses have shown great strength as well extraordinary
corrosion resistance, even better than high alloy containing stainless steels [3]. On the
contrary, metallic glasses as a whole show very little tensile ductility even though it
has extremely high (~ few GPa) yield strength. However, considerable compressive
plasticity has been noticed in many metallic glasses[4]. Therefore, structural
application of glassy alloys has been thought to be realised if it is used as corrosion
resistance coating. That would allow the common engineering alloys to get excellent
corrosion resistant to the order of stainless steel and hard coating without using costly
alloying elements as used in stainless steel. Accordingly research on the application of
corrosion resistant amorphous and nanocrystallinecoating has gone up too.
In this aspect, it is important to mention that it is not all the time necessary that
homogeneous amorphous metallic glass structure would give excellent corrosion
resistance. It is generally thought that since homogeneous glass has no grain
boundary, it would have excellent corrosion resistance. However, there are instances
where partially (other part is amorphous) or fully nanocrystalline structure can give
better corrosion resistance than the fully amorphous structure [5], [6]. Hence, even if
the coating is partially crystalline, coating can possess great corrosion resistance.
The Fe based glassy alloys reported in literature are manufactured from liquid
melt of high purity Fe (~ >99% wt%) mixed with high purity elemental powder of other
alloys.
Prior Art:
1. Title: High-carbon iron-based amorphous alloy using molten pig iron and
method of manufacturing the same
Inventors: Sang-Won Kim, Gab-SikByun, Young-Geun Son, Eon-Byeong Park, Sang-
Hoon Yoon, Sang-Wook Ha, Oh-Joon Kwon, Seung-Dueg Choi, SeongHoon Yi, US
Patent No. 9222157, Dec. 29, 2015.
This invention presents that molten pig iron from blast furnace can be used to make
high carbon iron-based amorphous alloy.Further, they showed that the glass forming
ability is increased by addition of at least any one of the ferroalloys used in steel
making processes like ferro-boron, ferro-phosphorous, ferro-silicon, and ferro-chrome
to the molten pig iron.
Comparison-In this technique, the glass forming compositions selected arbitrarily and
require experimental validation to prove the glass forming nature of the selected
composition. The minimum carbon content is maintained at 13.5 at%.
2.Title: Fe-based bulk amorphous alloy compositions containing more than 5
elements and composites containing the amorphous phase
Inventors: LichengXun, Li Hongxiang, a Xu Ming, Li Zhongzhe, Yudong Chen, right
Chin Cheung, Jin Zhe right Admiralty yuan, Huang Renx, US Patent No. 7815753,
Oct.19,2010.
In this invention,Fe-based amorphous base alloy is produced by mixing ferro-
phosphorous and ferro-boron with cast iron containing at least 2 at % silicon. Further,
new glass forming alloys were made by trial and error method by alloying the base
Fe—C—Si—P—B alloy with Al, Cr, Nb, V, W, Nb-Mo, Ti-Al, and Cr-Al respectively.
Each glass forming compositions were made by arc melting and suction casting into 1
mm diameter and 45 mm in length and the glass forming ability is studied by
differential scanning calorimetry.
Comparison-
In this technique, the glass forming ability can be found only after making the alloy.
Since it is a trial and error method even though a particular composition may be found
to have glass forming characteristics but it may not be the best glass forming
composition in the particular alloy base. The minimum silicon content is maintained at
2.0 at%.
3.Title: Production of iron-boron-silicon composition for an amorphous alloy
without using ferro-boron
Inventors: Subhash C. Singhal US Patent No. 4602951, July. 25, 1986.
This invention consists of a process to produce aluminium-free iron-boron-silicon-
carbon based amorphous alloy for the magnetic application. In this process mixture of
iron oxide, ferro-silicon, carbon in iron is prepared then the mixture heated up to 1575
° C. Then the anhydrous B2O3 is added to the molten mixture at less than 1500 °C.
The anhydrous B2O3 is reduced by silicon and molten iron-3% boron-5% silicon is
produced with silicon dioxide containing slag. This process eliminates the usage of
expensive ferroboron alloying addition to maintaining the required boron level.
Comparison- This process requires complex equipments to make the amorphous
alloy. It can only be used to make iron-boron silicon based amorphous alloys.
OBJECTS OF THE DISCLOSURE:
In view of the foregoing limitations inherent in the prior-art, it is an objective of
the disclosure to maximize amount of high phosphorus containing blast furnace hot
metal to achieve cost effectiveness of the Fe based amorphous alloys.
Another objective is to achievecomposition of the amorphous alloys with the
enhancedglass forming ability.
Still another objective of the disclosure is that the external alloys should be minimum
to achieve the abovementioned objectives and cost effectiveness.
SUMMARY OF THE DISCLOSURE
The disclosurediscloses about the high phosphorous containing blast furnace
hot metalobtained as an output from commercial blast furnaces for synthesising
amorphous and nanocrystalline Fe-alloys. It also validates the thermodynamic
calculations in order to improve the glass forming ability of the high phosphorous blast
furnace hot metal with a minor adjustment of the composition by adding one or
combination of alloying elements, like P, B, Nb, Mo, Cr, etc. Moreover, the blast
furnace hot metal in the present case has higher P, as compared to the reported blast
furnace hot metal in different open reports.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWING:
Figure 1 illustrates relation between calculated mixing enthalpy, and normalised
mismatch entropy, for some of Fe based glassy alloys, Hot Metal, high P Hot Metal
and Hot Metalwith other alloy additions in accordance with embodiment of the
disclosure.
Figure2 illustrates relation between calculated mixing enthalpy, and PHSS for some of
the Fe based glassy alloys, Hot Metal, high P Hot Metal and Hot Metal with other alloy
additions in accordance with embodiment of the disclosure.
DETAILED DESCRIPTION OF THE DISCLOSURE:
Various embodiments of the disclosure provide an iron-based amorphous alloy
comprising:a blast furnace hot metal 75-100 (wt %) and rest alloying elements 0-25
(wt %), the alloying elements comprising at least one or in combinations of
phosphorus (P), niobium (Nb), chromium (Cr), molybdenum (Mo) and boron (B) and
the blast furnace hot metal comprising Carbon (C)- 3.5-4.0, phosphorus (P)- 1.4-1.6,
silicon (Si)- 2.00, manganese (Mn)-0.5-0.7, sulphur (S)-0.030 and rest iron (Fe), all in
wt %.
However, as per the present disclosure, inventors propose to use blast furnace
hot metal in varying proportions as starting liquid melt and convert it into glassy alloys
of varying glass forming ability by addition minor alloying additions and modification of
composition. Hence, the present disclosure tries to see the potential of formation of
glassy alloys using the blast furnace hot metal and subsequent modification of
composition of the blast furnace hot metal by doing a series of alloy design via the
routes as stated in subsequent discussion. High ‘P” hot metal is a product from blast
furnace. It contains high amount of carbon, phosphorous, silicon, manganese, etc.
An iron-based amorphous alloy comprises blast furnace hot metal 75-100
(wt%) and rest alloying elements 0-25 (wt%).The said alloying elements comprises
alone or in combination of phosphorus (P), niobium (Nb), chromium (Cr), molybdenum
(Mo) and boron (B).
The said blast furnace hot metal comprises(in at.%) carbon (C)- 14.04,
phosphorus (P)- 2.18, silicon (Si)- 3.43, manganese (Mn)-0.44, sulphur (S)-0.00 and
iron (Fe)-79.91.
One typical composition is cited in Table 1. Conventionally the blast furnace hot
metal is then subjected to steel making in LD converter. The current proposition
eliminates the requirement of high purity alloying elements for making Fe-based
metallic glass as generally followed in reported literatures. It can bring down the cost
of the overall alloy and makes it viable to produce metallic glasses cheaper. Most
important aspect of the disclosure can enable for use of low cost glassy alloy powders
of varying degree of glass forming ability made from blast furnace hot metal for further
using as raw material for coating to achieve higher corrosion and wear resistance
properties.
Typical compositions of blast furnace hot metal are shown in Table 1.
Table 1
In order to
understand the glass formation in a particular alloy system, it is important to
understand the glass forming ability (GFA) of the particular composition. Recently,
Chattopadhyaya et al. [8] have put up a review article, where it has been clearly
shown that there could be semi-predictive as well predictive approaches in order to
judge glass forming ability of a particular composition.
Inoue et al. [10] proposed three empirical rules for high glass forming ability
(GFA) in metallic glasses:
(i) The atomic size difference between major constituents must be >12%,
(ii)there must be a negative mixing enthalpy between constituents, and
(iii)the alloy composition must include more than three elements.
Glass forming ability (GFA) of an alloy composition determines its ability to
transform into the glassy state from crystalline state. In case of thin ribbon glasses
produced through rapid solidification processes (RSP) or Bulk Metallic Glasses
(BMG), GFA of an alloy systems can be predicted to a reasonable accuracy with
experimental validation. The Fe based metallic glasses showing good GFA and
produced in the form of thin ribbon can be broadly classified into the metal–metalloid
and metal–metal systems. The metal can be either just Fe or a combination of other
metallic elements and similarly, the metalloid element also can be either just one or a
combination of more than one metalloid element. The metal–metalloid systems
typically contain 80 at% metal and 20 at% of metalloid.
The typical metalloid elements added here are B, C, P and Si, with their total content
amounting to nearly 20 at%. The metal element in metal-metalloid or metal-metal
glass systems can be either only Fe or a mixture of different Fe-group elements like
Co and/or Ni. Other metallic elements like Cr, Mn, Al, Ga, Mo, Zr, Nb and Ta are also
added, with their concentrations ranging from 2–20 at%.
Unlike thin ribbon glasses, Fe based BMGs reported so far are of the metal–metalloid
type. Though, these BMGs typically contain similar metal-metalloid elemental
combinations like ribbon glasses but to enhance the GFA of these alloys further,
addition of special alloying elements like Ln, Ga, Zr, Nb and Mo with significant atomic
size difference and large negative heat of mixing between Fe and the metalloids (P, C,
B and/or Si) and rare-earth elements like Y, Er, Gd and Tm are also reported in
literatures. Accordingly the Fe-based BMGs can be classified into three broad groups
like: Fe–M–(P,C,B,Si) (M = Al, Ga, Mo); Fe–B–Si–Nb based; and Fe–Cr–Mo–C–B–Ln
[14].
Thermodynamic and Topological parameters for evaluating Glass formability
Higher Glass forming ability indicates that the glass can be formed at lower
critical cooling rate with higher section thickness while cooling from liquid state [8].
From thickness data, it is very clear that the existing better Fe-based glassy alloys
(Ref. Table 2) from literature have very good glass forming ability (GFA) and they are
bulk glass formers too (thickness > 1mm). The important parameters to evaluate GFA
of metallic glasses are chemical mixing enthalpy (AHchem) , mismatch entropy
normalised by Boltzmann constant (salloy/kB) [7] and further a much better
parameter is PHSS, which has strong correlation with GFA of a glassy alloy [13].
While designing different combination of compositions using blast furnace hot
metal with other minor alloying addition these parameters have been considered.
Mismatch entropy normalised by Boltzmann constant (salloy/kB) and chemical mixing
enthalpy (AHchem) correspond to the rule (i) and (ii) of the empirical rules.Critical value
of chemical mixing enthalpy (AHchem)is -15 KJ/moland of mismatch entropy
normalised by Boltzmann constant (sfoy/kB) is 0.1 to obtain high GFA for typical
multicomponent systems [7] . But these parameters were limited to ternary alloy
system onlyand found to be insufficient to determine GFA in multicomponent systems.
However,PH55 parameter gives much more quantitative analysis of GFA in
multicomponent systems[13].
Mixing enthalpy:
ΔH chem is calculated using Miedema’s semi-empirical mode [9].
AHchemis chemical mixing enthalpy and Oij is regular solution model interaction
parameter between i-th and j-th component. ntJ = 4xAH^x, where AH^X is mixing
enthalpy of A and B resulting from Miedema’s macroscopic model for binary alloys. Ci
is composition of i-th element
Mismatch entropy:
The mismatch entropy arises due to the atomic size difference of the constituting
elements in the alloy system is calculated using Mansoori empirical model [10].
£ =1/(1- £) where
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