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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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Patent Information

Application #
Filing Date
10 March 2017
Publication Number
37/2018
Publication Type
INA
Invention Field
METALLURGY
Status
Email
ipo@knspartners.com
Parent Application
Patent Number
Legal Status
Grant Date
2024-02-28
Renewal Date

Applicants

TATA STEEL LIMITED
RESEARCH AND DEVELOPMENT AND SCIENTIFIC SERVICES DIVISION, JAMSHEDPUR-831001, JHARKHAND, INDIA
INDIAN INSTITUTE OF TECHNOLOGY, KANPUR
KANPUR, UTTAR PRADESH - 208016, INDIA

Inventors

1. Atanu Banerjee
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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Application Documents

# Name Date
1 201731008474-FORM 4 [18-04-2025(online)].pdf 2025-04-18
1 Power of Attorney [10-03-2017(online)].pdf 2017-03-10
2 201731008474-FORM 4 [12-08-2024(online)].pdf 2024-08-12
2 Form 5 [10-03-2017(online)].pdf 2017-03-10
3 Form 3 [10-03-2017(online)].pdf 2017-03-10
3 201731008474-IntimationOfGrant28-02-2024.pdf 2024-02-28
4 Form 20 [10-03-2017(online)].pdf 2017-03-10
4 201731008474-PatentCertificate28-02-2024.pdf 2024-02-28
5 Form 1 [10-03-2017(online)].pdf 2017-03-10
5 201731008474-Written submissions and relevant documents [14-02-2024(online)].pdf 2024-02-14
6 Drawing [10-03-2017(online)].pdf 2017-03-10
6 201731008474-Correspondence to notify the Controller [25-01-2024(online)]-1.pdf 2024-01-25
7 Description(Complete) [10-03-2017(online)].pdf_200.pdf 2017-03-10
7 201731008474-Correspondence to notify the Controller [25-01-2024(online)].pdf 2024-01-25
8 Description(Complete) [10-03-2017(online)].pdf 2017-03-10
8 201731008474-FORM-8 [24-01-2024(online)].pdf 2024-01-24
9 201731008474-US(14)-ExtendedHearingNotice-(HearingDate-30-01-2024).pdf 2024-01-15
9 Form 18 [18-04-2017(online)].pdf 2017-04-18
10 201731008474-FORM 13 [13-12-2023(online)].pdf 2023-12-13
10 Other Patent Document [17-05-2017(online)].pdf 2017-05-17
11 201731008474-FORM-26 [24-10-2018(online)].pdf 2018-10-24
11 201731008474-RELEVANT DOCUMENTS [13-12-2023(online)].pdf 2023-12-13
12 201731008474-FER.pdf 2020-07-15
12 201731008474-Written submissions and relevant documents [13-12-2023(online)].pdf 2023-12-13
13 201731008474-FER_SER_REPLY [28-12-2020(online)].pdf 2020-12-28
13 201731008474-FORM-26 [28-11-2023(online)].pdf 2023-11-28
14 201731008474-CLAIMS [28-12-2020(online)].pdf 2020-12-28
14 201731008474-Correspondence to notify the Controller [27-11-2023(online)].pdf 2023-11-27
15 201731008474-RELEVANT DOCUMENTS [27-01-2023(online)].pdf 2023-01-27
15 201731008474-US(14)-HearingNotice-(HearingDate-28-11-2023).pdf 2023-10-31
16 201731008474-FORM 13 [27-01-2023(online)].pdf 2023-01-27
16 201731008474-POA [27-01-2023(online)].pdf 2023-01-27
17 201731008474-POA [27-01-2023(online)].pdf 2023-01-27
17 201731008474-FORM 13 [27-01-2023(online)].pdf 2023-01-27
18 201731008474-RELEVANT DOCUMENTS [27-01-2023(online)].pdf 2023-01-27
18 201731008474-US(14)-HearingNotice-(HearingDate-28-11-2023).pdf 2023-10-31
19 201731008474-CLAIMS [28-12-2020(online)].pdf 2020-12-28
19 201731008474-Correspondence to notify the Controller [27-11-2023(online)].pdf 2023-11-27
20 201731008474-FER_SER_REPLY [28-12-2020(online)].pdf 2020-12-28
20 201731008474-FORM-26 [28-11-2023(online)].pdf 2023-11-28
21 201731008474-FER.pdf 2020-07-15
21 201731008474-Written submissions and relevant documents [13-12-2023(online)].pdf 2023-12-13
22 201731008474-FORM-26 [24-10-2018(online)].pdf 2018-10-24
22 201731008474-RELEVANT DOCUMENTS [13-12-2023(online)].pdf 2023-12-13
23 201731008474-FORM 13 [13-12-2023(online)].pdf 2023-12-13
23 Other Patent Document [17-05-2017(online)].pdf 2017-05-17
24 Form 18 [18-04-2017(online)].pdf 2017-04-18
24 201731008474-US(14)-ExtendedHearingNotice-(HearingDate-30-01-2024).pdf 2024-01-15
25 Description(Complete) [10-03-2017(online)].pdf 2017-03-10
25 201731008474-FORM-8 [24-01-2024(online)].pdf 2024-01-24
26 Description(Complete) [10-03-2017(online)].pdf_200.pdf 2017-03-10
26 201731008474-Correspondence to notify the Controller [25-01-2024(online)].pdf 2024-01-25
27 Drawing [10-03-2017(online)].pdf 2017-03-10
27 201731008474-Correspondence to notify the Controller [25-01-2024(online)]-1.pdf 2024-01-25
28 Form 1 [10-03-2017(online)].pdf 2017-03-10
28 201731008474-Written submissions and relevant documents [14-02-2024(online)].pdf 2024-02-14
29 Form 20 [10-03-2017(online)].pdf 2017-03-10
29 201731008474-PatentCertificate28-02-2024.pdf 2024-02-28
30 Form 3 [10-03-2017(online)].pdf 2017-03-10
30 201731008474-IntimationOfGrant28-02-2024.pdf 2024-02-28
31 201731008474-FORM 4 [12-08-2024(online)].pdf 2024-08-12
31 Form 5 [10-03-2017(online)].pdf 2017-03-10
32 201731008474-FORM 4 [18-04-2025(online)].pdf 2025-04-18
32 Power of Attorney [10-03-2017(online)].pdf 2017-03-10

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