**3.4 Technological development strategy analysis: analysis of the top five patent families**

The analysis of the top five patent families is shown in **Table 3**. The first patent family, US2009236017A1 [33], proposes an apparatus and method comprising


#### **Table 2.**

*Trend of the patent applications for top ten patent assignees.*


#### **Table 3.**

*Top five patent families.*

uniform heating, rheological softening, and thermoplastic forming of metallic glasses rapidly into a net shape using a rapid capacitor discharge forming (RCDF) tool. The RCDF method utilizes a discharge of electrical energy stored in a capacitor to uniformly and rapidly heat a sample or charge of metallic glass alloy to a predetermined "process temperature" between the glass transition temperature of the amorphous material and the equilibrium melting point of the alloy on a time scale of several milliseconds or less. Once the sample is uniformly heated such that the entire sample block has a sufficiently low process viscosity, it may be shaped into high-quality amorphous bulk articles by any number of techniques, such as injection molding, dynamic forging, stamp forging, and blow molding, in a time frame of less than 1 s. The second patent family, US7323071B1 [34], discloses a metallic glass coating formed over a metallic substrate. After the formation of the coating, at least a portion of the metallic glass can be converted into a crystalline material having a nanocrystalline grain size. The third patent family, US5628840 [35], relates to a glassy metal alloy consisting essentially of the formula FeaCobNicMdBeSifCg, where "M" is at least one member selected from the group consisting of molybdenum, chromium, and manganese. The notations "a–g" are in atom percent, "a" ranges from about 30 to about 45, "b" ranges from about 4 to about 40, "c" ranges from about 5 to about 45, "d" ranges from about 0 to about 3, "e" ranges from about 10 to about 25, "f" ranges from about 0 to about 15, and "g" ranges from about 0 to about 2. The alloy can be cast by rapid solidification into a ribbon or otherwise formed into a marker that is especially suited for use in magneto-mechanically actuated article surveillance systems. Advantageously, the marker is characterized by relatively linear magnetization response in the frequency regime wherein harmonic marker systems operate magnetically. Voltage amplitudes detected for the marker are high, and interference between surveillance systems based on mechanical resonance and harmonic re-radiance is virtually eliminated. The fourth patent family, US6183568B1 [36], proposes a soft magnetic thin microcrystalline film of FeaBbNc (at %) where B is at least one of Zr, Hf, Ti, Nb, Ta, V, Mo, and W, and 0 < b ≦ 20 and 0 < c ≦ 22, except for the range of b ≦ 7.5 and c ≦ 5, show low coercivity Hc of 80–400 Am<sup>−</sup><sup>1</sup> (1–5 Oe), which is stable upon heating at elevated temperature for glass bonding. This film is produced by crystallizing an amorphous alloy film of a similar composition at 350–650°C to a crystal grain size of up to 30 nm to provide uniaxial anisotropy and increased magnetic permeability at the higher frequency. It can also provide low magnetostriction of around λs = 0. The composite magnetic head is made using this thin film. A diffusion-preventive SiO2 layer disposed between the ferrite core, and this thin film in the magnetic head prevents an interdiffusion layer and suppresses beats in the output signal. The fifth

**69**

*Insight into Bulk Metallic Glass Technology Development Trajectory: Mapping from Patent…*

metallic glass composition comprising at least Fe, Mo, P, C, and B, where

**3.5 Technological exploitation analysis: five most-cited patents**

patent family, US8529712B2 [37], relates to an iron-based bulk metallic glass alloy and more particularly to a family of the iron-based phosphor-containing bulk metallic glass alloys exhibiting low shear moduli. The independent claim specifies an Fe-based

Fe comprises an atomic percent of at least 60, Mo comprises an atomic percent of 2–8, P comprises an atomic percent of 5–17.5, C comprises an atomic percent of 3–6.5, and B comprises an atomic percent of 1–3.5, wherein the composition has a shear modulus (G) of less than 60 GPa and a glass transition temperature (Tg) of less than 440° C, and the composition is capable of forming a bulk amorphous object having a critical

In most scientific publications, patents are rarely cited in SCI papers. For example, only about 1.5% of US patents are cited in SCI journals [38]. Similarly, in most technology fields, most of the prior art cited within patents are also patent documents, not scientific papers, which could be a sign of the few connections between academia and industry [38, 39]. However, the technological value of patents can provide important information to subsequent researchers and thus is worthwhile to refer to, especially in the case of patents with a high number of citations. Therefore, like a scientific paper, a high number of citations represent the high technological value of a patent, which might indicate that high commercial profit can be expected. In the present study, the five most-cited patents were extracted from the original patent pool (**Table 4**), and their technological contents

The most-cited patent in **Table 4**, US5288344, is about beryllium-bearing amorphous metallic alloy formed with a low cooling rate [40]. In this patent, the proposed technology suggests an alloy containing beryllium in the range of 5–52 atomic percent and at least one early transition metal in the range of 30–75 atomic percent and at least one late transition metal in the range of 2–52 atomic percent. A preferred group of metallic glass alloys has the formula (Zr1-xTix)a(Cu1-yNiy)bBec. A preferred embodiment is a class of alloys which form metallic glass upon cooling below the

at least quinary alloys that form metallic glass upon cooling below the glass transi-

alloys

US5368659 [42] / Cal. Inst. Tech. (US) Method of forming beryllium bearing

US5618359 [43] / Cal. Inst. Tech. (US) Metallic glass alloys of Zr, Ti, Cu, and Ni

US5735975 [41] / Cal. Inst. Tech. (US) Quinary Metallic glass alloys 220 / (7)

metallic glass

compositions

by low cooling rates

Nickel-based amorphous alloy

K/s, which is far below the nor-

**(Patent family)**

290 / (12)

204 / (12)

169 / (7)

157 / (4)

K/s. The second most-cited patent, US5735975, describes

**Title Times Cited/** 

Beryllium bearing amorphous metallic

K/s [41]. Such alloys comprise zirconium

*DOI: http://dx.doi.org/10.5772/intechopen.81733*

thickness of at least 2 mm.

are reviewed as follows.

mal cooling rate, 104

(US)

(KR)

*Top five patent families.*

**Table 4.**

**Patent number [reference]/ assignee (nationality)**

US5288344 [40] / Cal. Inst. Tech.

US6325868 [44] / Univ. Yonsei Seoul

glass transition temperature at a rate of less than 103

to 106

tion temperature at a rate of less than 103

*Insight into Bulk Metallic Glass Technology Development Trajectory: Mapping from Patent… DOI: http://dx.doi.org/10.5772/intechopen.81733*

patent family, US8529712B2 [37], relates to an iron-based bulk metallic glass alloy and more particularly to a family of the iron-based phosphor-containing bulk metallic glass alloys exhibiting low shear moduli. The independent claim specifies an Fe-based metallic glass composition comprising at least Fe, Mo, P, C, and B, where Fe comprises an atomic percent of at least 60, Mo comprises an atomic percent of 2–8, P comprises an atomic percent of 5–17.5, C comprises an atomic percent of 3–6.5, and B comprises an atomic percent of 1–3.5, wherein the composition has a shear modulus (G) of less than 60 GPa and a glass transition temperature (Tg) of less than 440° C, and the composition is capable of forming a bulk amorphous object having a critical thickness of at least 2 mm.

## **3.5 Technological exploitation analysis: five most-cited patents**

In most scientific publications, patents are rarely cited in SCI papers. For example, only about 1.5% of US patents are cited in SCI journals [38]. Similarly, in most technology fields, most of the prior art cited within patents are also patent documents, not scientific papers, which could be a sign of the few connections between academia and industry [38, 39]. However, the technological value of patents can provide important information to subsequent researchers and thus is worthwhile to refer to, especially in the case of patents with a high number of citations. Therefore, like a scientific paper, a high number of citations represent the high technological value of a patent, which might indicate that high commercial profit can be expected. In the present study, the five most-cited patents were extracted from the original patent pool (**Table 4**), and their technological contents are reviewed as follows.

The most-cited patent in **Table 4**, US5288344, is about beryllium-bearing amorphous metallic alloy formed with a low cooling rate [40]. In this patent, the proposed technology suggests an alloy containing beryllium in the range of 5–52 atomic percent and at least one early transition metal in the range of 30–75 atomic percent and at least one late transition metal in the range of 2–52 atomic percent. A preferred group of metallic glass alloys has the formula (Zr1-xTix)a(Cu1-yNiy)bBec. A preferred embodiment is a class of alloys which form metallic glass upon cooling below the glass transition temperature at a rate of less than 103 K/s, which is far below the normal cooling rate, 104 to 106 K/s. The second most-cited patent, US5735975, describes at least quinary alloys that form metallic glass upon cooling below the glass transition temperature at a rate of less than 103 K/s [41]. Such alloys comprise zirconium


**Table 4.** *Top five patent families.*

*Solid State Physics - Metastable, Spintronics Materials and Mechanics of Deformable...*

US2009236017A1 [33]/Cal. Inst. Tech. (US) Forming of metallic glass by rapid capacitor

US5628840 [35]/Allied Signal INC. (US) Metallic glass alloys for mechanically

discharge

a substrate

**Title Patent** 

Method for preparing a magnetic thin film 25

Tough iron-based bulk metallic glass alloys 21

Method for forming a hardened surface on

resonant surveillance systems

**Families**

57

33

29

**Patent number [reference]/ assignee (nationality)**

LLC. (US)

Co. LTD (JP)

Tech. (US)

*Top five patent families.*

**Table 3.**

US7323071B1 [34]/Bechtel BWXT Idaho,

US6183568B1 [36]/Fuji Photo Film

US8529712B2 [37]/Cal. Inst.

uniform heating, rheological softening, and thermoplastic forming of metallic glasses rapidly into a net shape using a rapid capacitor discharge forming (RCDF) tool. The RCDF method utilizes a discharge of electrical energy stored in a capacitor to uniformly and rapidly heat a sample or charge of metallic glass alloy to a predetermined "process temperature" between the glass transition temperature of the amorphous material and the equilibrium melting point of the alloy on a time scale of several milliseconds or less. Once the sample is uniformly heated such that the entire sample block has a sufficiently low process viscosity, it may be shaped into high-quality amorphous bulk articles by any number of techniques, such as injection molding, dynamic forging, stamp forging, and blow molding, in a time frame of less than 1 s. The second patent family, US7323071B1 [34], discloses a metallic glass coating formed over a metallic substrate. After the formation of the coating, at least a portion of the metallic glass can be converted into a crystalline material having a nanocrystalline grain size. The third patent family, US5628840 [35], relates to a glassy metal alloy consisting essentially of the formula FeaCobNicMdBeSifCg, where "M" is at least one member selected from the group consisting of molybdenum, chromium, and manganese. The notations "a–g" are in atom percent, "a" ranges from about 30 to about 45, "b" ranges from about 4 to about 40, "c" ranges from about 5 to about 45, "d" ranges from about 0 to about 3, "e" ranges from about 10 to about 25, "f" ranges from about 0 to about 15, and "g" ranges from about 0 to about 2. The alloy can be cast by rapid solidification into a ribbon or otherwise formed into a marker that is especially suited for use in magneto-mechanically actuated article surveillance systems. Advantageously, the marker is characterized by relatively linear magnetization response in the frequency regime wherein harmonic marker systems operate magnetically. Voltage amplitudes detected for the marker are high, and interference between surveillance systems based on mechanical resonance and harmonic re-radiance is virtually eliminated. The fourth patent family, US6183568B1 [36], proposes a soft magnetic thin microcrystalline film of FeaBbNc (at %) where B is at least one of Zr, Hf, Ti, Nb, Ta, V, Mo, and W, and 0 < b ≦ 20 and 0 < c ≦ 22, except for the range of b ≦

7.5 and c ≦ 5, show low coercivity Hc of 80–400 Am<sup>−</sup><sup>1</sup>

heating at elevated temperature for glass bonding. This film is produced by crystallizing an amorphous alloy film of a similar composition at 350–650°C to a crystal grain size of up to 30 nm to provide uniaxial anisotropy and increased magnetic permeability at the higher frequency. It can also provide low magnetostriction of around λs = 0. The composite magnetic head is made using this thin film. A diffusion-preventive SiO2 layer disposed between the ferrite core, and this thin film in the magnetic head prevents an interdiffusion layer and suppresses beats in the output signal. The fifth

(1–5 Oe), which is stable upon

**68**

and/or hafnium in the range of 45–65 atomic percent, titanium and/or niobium in the range of 4–7.5 atomic percent, and aluminum and/or zinc in the range of 5–15 atomic percent. The balance of the alloy composition comprises copper, iron, cobalt, and nickel. The composition is constrained such that the atomic percent of iron is less than 10%. Furthermore, the ratio of copper to nickel and/or cobalt is in the range of 1:2 to 2:1. Therefore, the alloy glass can be formed at a reduced critical cooling rate without any beryllium addition. The third most-cited patent, US5368659, discloses an invention similar to the above most-cited patent; the alloy forms metallic glass containing beryllium in a narrower range of 2–47 atomic percent, at least one early transition metal in the range of 30–75 atomic percent, and at least one late transition metal in the range of 5–62 atomic percent [42]. Furthermore, the critical cooling rate to achieve the amorphous structure can be reduced to 1–100 K/s or lower. Patent US6325868, the fifth most-cited patent, discloses a nickel-based amorphous alloy composition, particularly a quaternary nickel-based amorphous alloy containing nickel, zirconium, and titanium as the main constituent elements and additive Si or P [44]. The quaternary nickel-zirconium-titanium-phosphorus alloy compositions comprise nickel in the range of 50–62 atomic percent, zirconium and titanium in the range of 33–46 atomic percent, and phosphorus in the range of 3–8 atomic percent, represented by the general formula Nid(Zr1−yTiy)ePf. The nickelbased amorphous alloy compositions have a superior amorphous phase-forming ability, and bulk amorphous alloy having a thickness of 1 mm can be produced by general casting methods.
