(12) INTERNATIONALAPPLICATIONPUBLISHED UNDERTHEPATENTCOOPERATIONTREATY(PCT) (19)WorldIntellectualPropertyOrganization InternationalBureau (43)InternationalPublicationDate 26May2011 (26.05.2011)

Published: (74) Agent: ROBIC; 1001, Square-Victoria, Bloc E - 8th Floor, Montreal (Quebec) H2Z2B7 (CA). with internationalsearch report(Art. 21(3)) (81) Designated States (unless otherwise indicated,for every kindof nationalprotection available): AE, AG, AL, AM, 

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- - - - (51) InternationalPatentClassification: C21D 9/573 (2006.01) C22C45/02 (2006.01) C21D 1/42(2006.01) (21) InternationalApplicationNumber: PCT/CA20I0/001844 (22) InternationalFilingDate: 18November2010 (18.11.2010) (25) FilingLanguage: English (26) PublicationLanguage: English (30) PriorityData: 61/262,603 19November2009 (19.11.2009) US (71) Applicant (for all designated States except US): HYDRO-QUEBEC [CA/CA]; 75, boul.**Rell(~-Levesque** Ouest, 22eEtage, Montreal (Quebec) H2Z IA4 (CA). (72) Inventors; and (75) Inventors/Applicants (for US only): FRANCOEUR, Bruno [CA/CA]; 971 Galilee, Beloeil(Quebec) BG6MI (CA). COUTURE, Pierre [CA/CA]; 1027, Jean-Bochart, Boucherville(Quebec)J4B 4A4 (CA). AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, CA,CH,CL,CN,CO, CR,CU, CZ,DE,DK,DM,DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ill, IL, IN, IS, JP, KE, KG, KM, KN, KP, KR,KZ,LA,LC, LK,LR,LS, LT,LU, LY,MA,MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO,NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH,n, TM, TN, TR, TT,TZ,UA, UG,US, UZ, VC,VN, ZA,ZM, ZW. (84) Designated States (unless otherwise indicated,for every kindof regionalprotection available): ARIPO (BW, GH, GM, KE, LR, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, ZW), Eurasian(AM, AZ, BY, KG, KZ, MD, RU,n, TM), European(AL, AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, MC, MK, MT,NL,NO, PL, PT, RO, RS, SE, SI, SK, SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, ML, MR,NE, SN, TD, TG). DeclarationsunderRule4.17:
as to applicant's entitlementto applyfor andbe granted apatent(Rule4.17(ii))

(54) Title: SYSTEMANDMETHODFORTREATINGANAMORPHOUS ALLOYRIBBON

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4 FIGURE 1
(57) Abstract: Amethodandasystemforcontinuouslyin-lineannealing aforwarding ferromagnetic amorphous alloyribbonina curved shape to improve its magnetic properties without causing the ribbon to become brittle and which operates at significant highribbon feeding rates. The amorphous alloyribbon is fed forward, tensioned and guided along apath at apresetfeeding rate andisheatedatapointalongthepathatarategreaterthan 103°C/secto atemperaturetoinitiateathermaltreatment. Thentheribbonis initially cooled at arate greaterthan 103°C/sec untilthethermaltreatment ends. Duringthethermaltreatment, a series of mechanical constraints is applied ontheribbon until the amorphous alloyribbon adopts a specific shape atrest afterthe thermal treatmentis ended. Aftertheinitialcooling,the amorphous alloyribbonis subsequentlycooledatasufficientrateto atemperature thatwillpreservethe specific shape.WO 2011/060546 PCT/CA2010/001844 

### 1 SYSTEM AND METHOD FOR TREATING AN AMORPHOUS ALLOY RIBBON
FIELD OF THE INVENTION
The present invention generally relates to amorphous materials. More particularly, it relates to a system and method for treating an amorphous alloy ribbon. More particularly, it also relates to a system and method for producing a magnetic core from atreated ductile amorphous alloy ribbon rolled up on a mandrel. 10 BACKGROUND OFTHE INVENTION
Iron-based amorphous alloys are sought for their soft magnetic properties in applications such as the manufacturing of distribution transformer cores, pulse power cores, and other item. Iron-based alloys in this document are mainly iron alloyed with various small percentages of other metals. They are manufactured by continuous rapid solidification of a stream of molten alloy cast at speeds approaching 100 km per hour. With casting cooling rates on the order of 106 °Celsius/second, the alloy atomic structure is solidified in a non-crystalline state 20 (amorphous). With the proper atomic composition, amorphous alloy ribbons having excellent soft magnetic properties can be produced. Particularly, they offer: a high magnetic induction saturation level, herein referred as 

### Bsat; a high permeability; a low coercive force; a low exciting power; and very low core loss. When designing distribution transformers, an alloy sheet candidate can be evaluated once it has been stacked or rolled upto form a core byconsidering the peak magnetic induction level Band associated core loss obtained ata peakapplied AC magneticfield up to 

### 80

### Aim, herein referred as 

### Bao. Properties obtained atvalues abovethis field, even if they are good, will require excessive exciting power thus, rendering the alloy less attractive. The magnetic properties ofamorphous alloys when the ribbon is stacked 30 or rolled uptoform acore can also be evaluated byconsidering their

### Bao/Bsat ratio. AWO 2011/060546 

### 2 PCT/CA2010/001844



### 8ao/8sat ratio close to 1 is sought for as it is indicative of an easy magnetization. A transformerproduced with a magnetic core having a high 8

### aowill be smallerand will cost less. As a rule of thumb, an amorphous alloy core having a 

### 8ao greater than about 1.3 Tesla is worth considering for replacing conventional grain-oriented 3% silicon steels in the manufacturing of distribution transformers. Additionally, ironbased amorphous alloys produce about one third ofthe core loss of silicon steels. Also, a single step continuous casting method for producing an amorphous alloy ribbon has the advantage of being simpler and cheaperwhen compared to casting, annealing, quenching, rolling, decarburising and coating steps involved in producing 10 a grain-oriented silicon steel sheet and which require larger equipments and more floor space. Iron-based amorphous alloys are the cheapest of all amorphous alloys because of the relative low cost for iron, its main constituent. With a rapid solidification process, the production of amorphous alloys is however limited to a very thin ribbon ofvarious widths. More handling is therefore required to stack the increased number of layers when building the magnetic cores. Moreover, magnetic properties of amorphous alloys are highly sensitive to internal mechanical stresses. Core loss and exciting powerdeteriorate in presence of random stresses in the alloy. The origin ofthese stresses is either residual or applied. Residual stresses appear during ribbon casting, and applied stresses are produced from external forces 20 imposed by bending or stacking the ribbon. These stresses must therefore be removed from the ribbon when it adopts afinal configuration into a core or, at least accommodated to a certain extent. Stress removal from the amorphous alloy ribbon is generally accomplished by annealing the material in a furnace at an elevated temperature for a predetermined amount of time. Also, the useful magnetic properties of iron-based amorphous alloy ribbons are obtained if, during the annealing treatment, the alloy is subjected to a uniform magnetic field or a tensile stress in direction ofthe ribbon longitudinal axis. Field or stress annealing reduces coercive forces and induces uniaxial magnetic anisotropy. With field annealing, the resulting magnetic anisotropy is oriented parallel to the applied field while with stress 30 annealing, it is either parallel or perpendicular depending on the alloy composition.WO 2011/060546 

### 3 PCT/CA2010/001844

Field or stress annealing will increase the Bao and Bao/Bsat ratio. Furnace annealing of amorphous alloy cores with an applied magnetic field following the flux path is widely used to produce enhanced magnetic cores for distribution transformers. The ribbon is positioned within the core to have its longitudinal axis oriented following the circulating path ofthe induced magneticflux.
When annealing an amorphous alloy, increasing the annealing temperature and annealing time will eventually lead to onset crystallization of its atomic structure and lost oftheir sought magnetic properties. Onset crystallization in amorphous alloys is 10 a temperature-time-transformation (TTT) phenomenon. For example, the time to onset crystallization at core operating temperatures in distribution transformers must be well above the time life of the transformers. In an annealing treatment, time to onset crystallization will be influenced bythe heating temperature rising rate, bythe annealing temperature level and soaking time, and bythe cooling temperaturefalling rate. High temperature heating and cooling rates combined with a short soaking time will allow use ofa higherannealing temperature.
The amorphous alloy ribbon Metglas 2605SA1, from Hitachi-Metals, having a nominal chemistry FeaoB11Sig, numbers being in atomic percent, is widely used in 20 many applications including transformers and inductors at electrical AC frequencies of 50 and 60 Hz. This alloy has a Bsat of 1.56 Tesla. When furnace annealed under an external applied magneticfield ortensile stress, the alloywill acquire an easyaxis ofmagnetization parallel to the applied field orstress. When the ribbon is stacked or rolled uptoform cores and then field annealed at350°C fortwo hours, the alloy has: a Bao of 1.49Tesla; a BaolBsat ratio of0.95; and the core loss is lowerthan 0.27W/kg at 60 HZ at a magnetic induction of 1.3 Tesla. These values were reported by the alloy manufacturer in an article entitled "Audible Noise From Amorphous Metal and Silicon Steel-Based Transformer Core", in IEEE Transactions on Magnetics, vol. 44, no. 11, 4104-4106, and in an article entitled: "Advances in amorphous and 30 nanocrystalline magnetic materials", published in Journal of Magnetism andWO 2011/060546 

### 4 PCT/CA2010/001844

Magnetic Materials, vol. 304, p. 187-191, 2006. Also, US patent 5873954 teaches that, in orderto benefit ofsuch low core loss, the 2605SA1 alloy must be annealed under an applied magneticfield fortwo hours at atemperature between 330°C and 380°C as depicted in Figure 2a. Minimal core loss is obtained at an annealing temperature between 350°C to 360°C. Alternatively, the patent points to some references where improvements of magnetic properties of amorphous alloys were obtained by stress-annealing. However, the sample configuration for tensile stress annealing in the mentioned references has invariably been aflat strip. Therefore, the authors of the patent consider use of stress annealing in the production of 10 amorphous alloy core transformers impracticable. Trying to furnace anneal the Metglas-SA1 alloy above 390°C will lead to onset crystallization of the alloy and thereby, to deterioration of the magnetic properties as reported by Hsu et al. in an article entitled: "Effect of the annealing Temperature on Magnetic property for Transformer with Amorphous Core", Proceeding of the 2009 8!h WSEAS International Conference on Instrumentation, Measurement, Circuit and Systems, page 171-175.
More recently in US patent application 2006/0180248, an iron-based amorphous alloy having a chemical composition FeaBbSicCd where 80<a<84, 8<b<18, 0<c::;5 20 and 0<d::;3, numbers being in atomic percent, was identified. The alloy achieves a saturation magnetic induction greater than 1.60 Tesla wherein the alloy is heattreated to be annealed atatemperaturefrom 300°C to 350°C which is lowerthan the temperature required for the 2605SA1 material. Included in the chemical composition, the new Metglas 2605HB1 alloy ribbon from Hitachi-Metals, having a nominal chemistry Fea1.8B15.aSi2.1Co.3, has a Bsa! of 1.65 Tesla. When the ribbon is stacked or rolled upto form cores and then field annealed at 320°C for one hour, the alloy has: a Bao of 1.55Tesla; a Bao/Bsa! ratio of0.95; and the core loss is lowerthan 0.24 W/kg at 60 HZ at a magnetic induction of 1.3 Tesla, which is an improvement over the commercially available SA1 material. These values were reported by the 30 alloy manufacturer in the articles cited above.WO 2011/060546 

### 5 PCT/CA2010/001844

However, furnace annealing of most iron-based amorphous magnetic alloy ribbons undesirably affects the ribbon mechanical structure. The furnace annealing treatmentweakens the alloywhich becomes brittle and therefore complicates ribbon handling. Furthermore, amorphous alloy cores remain highly sensitive to external stresses after annealing. Care must therefore be taken to limit these stresses in order to keep the performances within an acceptable limit. Metglas 2605SA1 and 2605HB1 are known to embrittle following conventional field furnace annealing processes and their magnetic properties areverysensitiveto applied stresses. 10 One known method for making a distribution transformer magnetic core with an amorphous alloy ribbon was disclosed by General Electric in many patents. US patents 4789849, 5050294, 5093981 and 5310975 disclose steps involved in the making of amorphous alloy rectangular-wound-cut core distribution transformers which address all ofthe particularities related to amorphous alloys mentioned above. Basically, multiple amorphous ribbons are simultaneously unrolled from supply coils, piled and then rolled up again together to produce a master coil. Then, multiple master coils are unrolled and piled to form a composite strip which is forwarded, stopped and held stationary while it is cut by shear blades into segments of 20 progressively reduced lengths which are successively stacked in appropriate staggered positions to produce a packet of composite strips. Multiple packets are then successively wrapped in piggyback on each other on a support frame. After sufficient numbers of packets have been wrapped, a conventional silicon steel sheet is wrapped around the formed core with both ends secured together. The frame is then removed and a second silicon steel sheet is affixed against the inner packet wall within the core window to prevent the core from collapsing internally. In the following step, the core is reformed into a rectangular shape with clamps and is secured in place with supporting members and straps, after which it is batch annealed in a furnace while applying an external magnetic field for a few hours. 30 When annealing is completed, a coating is applied on the lateral edges ofthe coreWO 2011/060546 6 PCT/CA2010/001844

except in the region where thejoints are located to secure the laminations together, and the strap and supporting members are removed. Finally, core lacing around the electrical coils is performed by manually opening the core to form a U-shape and by sliding the core through the window of preformed rectangular electrical coils and then re-forming the core into its rectangularshape by individuallyclosing and jointing the expanded lapped sets. Because the core laminations get brittle from the annealing process, core lacing around the electrical coils must be achieved with great care to ensure that no broken fragments find theirway into the electrical coils which could lead to short circuit failures. Overall, this known process for making a 10 rectangular-wound-cut core distribution transformerfrom an amorphous alloy ribbon involves agreat amount ofdiscontinuous steps, which require a lot oftime and floor space. Manufacturing ofsuch rectangular-wound-cut core distribution transformer is realized at the distribution transformer manufacturing plant. This contributes significantlyto increasetransformercosts.
An alternative for producing a distribution transformer core with an amorphous alloy ribbon is disclosed byAllan et al. in US patent 5566443. In this patent, a numberof electric coils are preformed, each having a portion with a shape of a sector of a circle. The preformed coils are then assembled together so that their portions 20 combine to form a circular limb and, in order to construct the magnetic core, a continuous thin amorphous alloy ribbon is rolled up on a circular hollow mandrel located around the circular limb to produce a circular core. Before being rolled up, the amorphous alloy ribbon has been previouslyannealed undermagneticsaturation on a second circular mandrel having the same external diameter as for the circular hollow mandrel, thus requiring atransfer ofthe annealed ribbon between mandrels. It is believed that the power loss associated with the cuts in the above known cut core transformer is avoided. Rolling-up-after-annealing ofan amorphous alloy ribbon will certainly introduce some stresses in the roll, which will introduce some additional core loss. However, it is believed that overall introduced stresses will be sufficiently 30 small such that a worthwhile advantage is achieved in having an amorphous alloyWO 2011/060546
7 PCT/CA2010/001844

circular-rolled-uncut core configuration. It is also believed that with a circular-rolleduncut core transformer, all of the above-mentioned disadvantages associated with making a rectangular-wound-cut core transformer are avoided. Furthermore, the circular core provides a shorter mean path length for the magnetic flux which reduces the core and coils sizes and weight. Although this transformer is simplerto produce than a cut core transformer, numerous discontinuous steps are still involved in the making ofthe core, which are: rolling uptoform acore; annealing the core in a furnace undermagneticsaturation; unrolling and rolling upthe ribbon again toform a core around a limb of the electrical coils. Also, direct transfer of the annealed 10 amorphous alloy ribbon will introduce unnecessary bending stresses which will cause increased core loss as the ribbon is not rolled up again at the same layer position in the circular core (the first outer layer becomes first inner layer and vice versa). This can be overcome bytransferring the ribbon on an intermediate mandrel first, as taught in US patent4906960 byAlexandrov but, this technique adds another step in the making ofthe core. Rolling-up-after-annealing of amorphous alloy circular cores as described above, although simple in appearance, remains a difficult task. The fact that the alloy becomes brittle when annealed for a significant amount of time makes it less 20 convenient when it needs to be rolled up again around a limb ofthe electrical coils. Silgailis et al. in US patent 4668309 demonstrated in Table 2 of the patent that in each attempt to unroll and roll up again an iron-based amorphous alloy ribbon of a furnace annealed circularcore weighting around 50 kg at speeds upto 0.3 meterper second, the ribbon broke more than 60 times. They also claimed in the disclosed invention that annealing the cores in a molten tin bath at a highertemperature for a shorter period of time does not degrade ductility as much as from conventional furnace annealing. Silgailis et al. showed in Table 2 that circular cores weighing around 18 kg and annealed bytheir method could be unrolled and rolled up again at a speed of 0.76 meter per second without breaking the ribbon more than 18 times. 30 Even if Silgailis et al. were able to significantly reduce the number of breaks withWO 2011/060546 

### 8 PCT/CA2010/001844

their annealing method, it remains unacceptable. Encountering just one ribbon breakage during rolling up can eject tiny fragments that will be scattered all around the assembly line and that may end up within the electrical coils, which then requires a stop in production for clean-up and a decision on whether or not the coils should be scrapped. The task becomes more difficultwhen rolling up ofthe ribbon must be performed first on an intermediate mandrel. Annealing-after-rolling of the core around the coils could overcome the problem, but this would require use of high temperature insulating materials in the coils which would render the transformer cost-prohibitive. Rolling-up-after-annealing and annealing-after-rolling of amorphous 10 alloy ribbon cores were both considered to produce large circular cores for a heavy ion fusion (HIF) driver. A HIF core must sustain a large flux swing in an extremely short amount of time which requires use of an inter-laminar insulation in the core. Even if rolling-up-after-annealing would avoid use of a high temperature insulating material, it was considered to be impractical due to the embrittlement ofthe ribbon and an annealing-after-rolling of a core incorporating a high temperature resistant insulation was rather adopted as reported in articles such as: "Induction Accelerator Development for Heavy Ion Fusion", L.L. Reginato, IEEE Proceedings of the 1993 Particle Accelerator Conference, vol. 1, p. 656
- 660, and : "Exciting New Coating For Amorphous Glass Pulse Cores", R.R. Wood, IEEE 1999 12th International 20 Pulsed Power Conference, vol. 1, p. 393
- 396, and: "Induction Core Alloys for Heavy-ion Inertial Fusion-energy Accelerators", A. W. Molvik, The American Physical Society, Physical Review Special Topics
- Accelerators and Beams, vol. 5, 080401, 2002. Production ofcircularcore distribution transformers made with rollingup-after-annealing of field furnace annealed amorphous alloy ribbon cores is impractical due to embrittlement of the alloy and therefore manufacturers are building field-furnace annealing rectangular-wound-cut core design as described above.

Thermal embrittlement of iron-based amorphous alloys induced by thermal 30 annealing has been a recurring problem for a long time as recently stated by KumarWO 2011/060546 

### 9 PCT/CA2010/001844

and al. in an article entitled: "Thermal embrittlement of Fe-based amorphous ribbons" published in 2008 in Journal of Non-Crystalline Solids, vol. 354, p. 882-888. Amorphous alloy ribbons show a ductile-to-brittle transition at a given temperature (Tdb

### O) belowwhich they are brittle and abovewhich they are ductile as reported in an article entitled: "Absence of Thermal Embrittlement in some Fe-B and Fe-Si-B Alloys", 

### A. R. Yavari, Materials Science and Engineering, vol. 98, p. 491-493, 1988. The fact that quenched iron-based amorphous alloy ribbons have a Tdbo lowerthan normal room temperature (20°C to 25°C) explains their ductility observed at normal room temperature. The degree of ductility at a given temperature can be estimated 10 by observing at which bending radius the ribbon breaks or cracks, or by observing how the ribbon responds to shear cutting or tearing. An annealed ribbon having a high degree of ductilitywould alleviate the breaking problem and could be rolled up afterannealing. Embrittlement ofmost iron-based amorphous alloy ribbons following thermal annealing is believed to be related to an increase of Tdboassociated to a temperature-time-transformation (TTT) dependent on the alloy composition. Keeping Tdb° below the handling temperature in order remain ductile is a target to achieve. Because the embrittlement an iron-based amorphous alloy is a TTT phenomenon during annealing, the degree of ductility of an annealed ribbon must therefore be evaluated once the core magnetic properties obtained following the annealing 20 treatment are satisfactory or within expected results, otherwise the annealing treatment is incomplete and the degree ofductility is misleading. Shorter annealing times at higher annealing temperatures are believed to yield amorphous alloy ribbons with greater ductility. Silgailis and al. showed with their iron-based amorphous alloy ribbon cores annealed in molten tin at a higher temperature for a shorter time that brittleness could be reduced. However, there is a limit in trying to shorten the annealing time due to a limit in heat transfer capacity within the core. Higher heattransfer capacity becomes possible by heat treating a single forwarded ribbon in-line along a portion ofitstravelling path.WO 2011/060546 10 PCT/CA2010/001844

In-line annealing ofamorphous alloy ribbon without thermal embrittlement has been explored. An understanding ofthe amorphous alloy, its annealing dynamics and its associated embrittlement has been proposed by Taub in an article entitled: "A New Method for Stress Relieving Amorphous Alloys to Improve Magnetic Properties", published in IEEE Transactions on Magnetics, vol. Mag-20, no. 4, July 1984, p 564- 569, and in US patent 4482402. The document gives a general description on the nature of amorphous alloys, the way they are produced, the good magnetic properties ofsome classes ofthese alloys for application in distribution transformers and most importantly, discloses the necessity of stress relieving the material to 10 benefit from its magnetic properties. According to Taub, mechanical stress relief in amorphous alloys is governed by flow and structural relaxation. Flow refers to homogeneous deformation in response to stress and structural relaxation is an atomicstructure change towards an equilibrium configuration. Taub states in column 4, lines 9 to 15, "I have found that the competing materialprocesses offlow and structuralrelaxation mustbe accountedforin orderto optimize the developmentof softmagneticproperties in amorphousmetals. Specifically, flowmustbe maximized and structural relaxation must be minimized. Once that state is obtained with the amorphousmetalin itsfinalshape, thatstatemustbepreserved."
20 A lowerviscosity at an elevated temperature in an amorphous alloy provides a low flow resistance, which allows stresses to be relieved but, on the other hand, is believed to allowstructural relaxation, which increases the viscositywith time atsaid temperature and therefore also increases the flow resistance as the atomic structure tends to adopt an equilibrium configuration. The temperature dependence belowTgO (glass transition temperature) of both the viscosity and the viscosity increase rate with time are believed to closelyfollow an Arrhenius law. The structural relaxation is considered as an unavoidable consequence of stress relief annealing, which is believed to be responsible for the embrittlement of the ribbon. Therefore, prior art suggests that it is desirable to stress relieve the amorphous alloy without allowing 30 too much structural relaxation in order to have an annealed ductile ribbon. ThisWO 2011/060546
11 PCT/CA2010/001844

would correspond to keep the resulting Tdbo increase below the ribbon's handling temperature.
Taub teaches that the onlyway to obtain benefits of minimized structural relaxation while stress relieving the alloy is to heat as rapidly as possible to a higherannealing temperature for a shorter time and to cool the alloy sufficiently rapidly from the annealing temperature to preventanysignificantadditional and detrimental structural relaxation. Taub also adds in column 10, lines 8to 13, that: "Itis essentialthat the ribbon not to be heated untilafterit has reached its final configuration; otherwise, 10 structural relaxation will commence before all the winding stresses have been applied[.

..]'.Structural relaxation is therefore believed to be a negative side effect of the amorphous alloy annealing process which can be minimized in rapid annealing conditions.
Taub disclosed a method and apparatus to perform in-line annealing on aforwarded ribbon of a predetermined shape. In his apparatus, a heat source, such as: heat beams; direct contact with a heating media; or resistance self-heating, heats a ribbon at a high temperature rising rate (more than 300°C/min) after it has attained its final configuration. The ribbon is then rapidly cooled (at least 100°C/min) by 20 supplying ajetofcooling medium, such as airoran inertgas like nitrogen orstreams of liquid quenchants, to the ribbon immediately afterthe ribbon exits the area ofthe heating region while still in its final configuration in order to freeze the as-annealed stress-free structure in the ribbon. The apparatus was tested on an iron-based amorphous alloy ribbon Fea1.sB14.sSi4 which was then rolled up to form a core. For ribbon feeding rates up to a maximum of 26 em/min (0.5 em/sec), reported results showacore loss lowerthan 0.28W/kg (0.13 W/lb) and an exciting power lowerthan 1.45 VA/kg (0.66 VA/lb) at an AC magnetic induction of 1.4 Tesla (14 kG) and a Bao/Bsat ratio (equivalent in the document to B1 /B100 using Oersted instead ofTesla) greater than 0.80. The reported Bao/Bsat ratio is good considering the presence of 30 some stresses in the roll. Above 26 em/min (0.5 em/sec), the magneticproperties getWO 2011/060546 12 PCT/CA2010/001844

worse. Taub also reports achieving heating rates of500ae/min. The resulting degree ofbrittleness orductilityofthe iron-based amorphous alloyspecimens annealed with this apparatus is notquantified.
Senno et al. in US patent 4288260 claimed an apparatus for heat-treating an amorphous alloy ribbon continuously fed under a tensile stress at a predetermined speed in the range of 1 to 50 em/sec with its surface sliding in contact against a stationary heating bodyorbeing pressed againstthe surface ofa heating roller byan urging roller, which can be replaced by another heating roller, to enhance the 10 magnetic properties and remove curlings of an amorphous alloy ribbon without causing anydevelopments ofbrittleness ofthe ribbon. In the examples 1 to 6, Senno et al. disclose results showing magnetic improvements for ribbons of given atomic compositions that were passed over a heated stationary body at feeding rates between 3.5 em/sec (1/v-0.28sec/cm) and 9.1 em/sec (1/v-0.11sec/cm). Magnetic improvements are also disclosed in example 7for aforwarded ribbon that has been pressed against the surface of a heating roller by another roller at a slowerfeeding rate of 1 em/sec (1/v-1sec/cm). This slower feeding rate is comprehensible as the pressed contact region between the two rollers is very small. No reference is made on using iron-based amorphous alloy compositions, as examples are shown onlyfor 20 cobalt-based alloys. No impacts on core loss, on exciting power, on the Bso, on the Bso/Bsat ratio and on the degree of brittleness ofan annealed iron-based amorphous alloy ribbon are quantified through experimental results. No comparison is madewith the furnace annealing method. Based on Figure 6, the heat treatment ofthe ribbon passed over a stationary heating body shows a deterioration of the coercive force with increase of ribbon speed above 10 em/sec (1/v-0.1sec/em). Also, no details are disclosed on heating rates and no references are made about the cooling stage as the ribbon is simplycollected on atake-up mandrel.
Gibbs discloses in UKpatent application GB 2148751 a method bywhich a length of 30 amorphous strip being rolled up onto a mandrel is simultaneously heated by a directWO 2011/060546 13 PCT/CA2010/001844

current passing through a portion ofthe strip that is approaching the mandrel. In this case, two spaced adjustable sliding contact electrodes (or one electrode and the mandrel) are used to supplythe current. The strip is heated byjoule losses from the flowing current and is either cooled before or after reaching the rolling point. However, no detailed information is disclosed on the configuration ofthe strip in the heat-treating and cooling zones otherthan optionally allowing the strip to coolon the mandrel. Gibbs only discloses reduced coercive forces measured on two non ironbased alloy samples forwarding respectively at 9 and 14 cm/sec and annealed with his method when compared to furnace annealing. There is no reference made on 10 heating and cooling rates, to the core loss, the exciting power, the BaD, the Bao/Bsat ratio, orthe brittleness ofthe annealed ribbon.


### Li et al. in the US patent 5069428 disclose an annealing method by which an amorphous ribbon slowlyforwarded is self-heated by applying an AC or pulsed high current through a ribbon passing between a pair of electrodes. The circulating current through the conducting resistance ofthe ribbon producesjoule heating. The current is passed through the ribbon while being maintained in a predetermined configuration. For a curved ribbon, the ribbon is passed over an insulated roller, preferably made of ceramic, with a pair of spring-loaded electrode rollers pressing 20 the ribbon respectively at the entry and exit point of the ribbon on the roller. In example 1, an iron-based amorphous alloy ribbon Fe78B138ig, alloy type 260582 known to have a Bsatof 1.56Tesla, annealed atafeeding rate of0.3 cm/secwith this process shows an improvement of the magnetic induction from 0.85 to 1.27 Tesla (8.5 to 12.7 kG) underan applied magneticfield of 160 Aim (2 De) compared to an as-cast specimen. The annealing embrittlement of the tested specimen has a fracture strain between 0.9 and 1 by bending test compared to 7x10 to 5x10 for furnace annealed samples. The document does not specify if the magnetic properties measurements were performed on a core oron a single ribbon. However, the resulting core loss is not clearly disclosed and no reference is made on the 30 exciting power. The iron-based samples annealed with this method has a BaD only atWO 2011/060546 14 PCT/CA2010/001844

about 1.0 Tesla as reported in Figure 4 (1 Oe

# =80 AIm) which gives a low 

### Bao/Bsat ratio of 0.64. Also, no information is disclosed on the heating rates and on howthe cooling is performed aftertreatment as the ribbon is simply collected onto atake-up mandrel. The authors claim a ribbon that can be annealed up to a feeding rate of 10em/secwith this method.
In French patent application FR 2673954, and in an article entitled "On the Optimization of Soft-Magnetic Properties of Metallic Glasses by Dynamic Current Annealing", IEEE Transaction on Magnetics, vol. 28, no. 4 1992, p. 1911-1916, 10 Perron et al. disclosed a joule heating apparatus similar to 

### Li et al. to anneal an amorphous alloy ribbon in a circular shape. The ribbon is passed over an insulated fixed drum or rotating roller, preferably made of quartz or alumina, with a pair of cooled copper electrodes contacting the ribbon respectively at the touching and separating point ofthe ribbon on the drum or roller. In addition to 

### Li et al.'s method, the cooled electrodes are used as a cooling means to freeze the stress relieved ribbon before it separates from the drum or roller. In example 1, an iron-based amorphous alloy ribbon, alloy type 2605S2, annealed at a feeding rate of 1 em/sec with this process shows an improvement ofthe magnetization curve compared to a furnace field annealed specimen as shown in Figure 5 of the patent. The applied 20 magnetic field is reduced to 10 AIm compared to 14 AIm at a measured magnetic induction of 1.0 Tesla. The document does not specify if the measurements were performed on a core or on a single ribbon. Perron et al. report an average heating and cooling rates of 70 CO/second achieved with this apparatus. They claim that, with their invention, a ribbon could be annealed at speeds near 1 em/sec. There is no reference made to the core loss, the exciting power, the 

### BaD, the 

### Bao/Bsat ratio, or the brittleness ofthe annealed ribbon.
Waeckerle et al. in US patent application US2008/0196795 disclosed a ribbon annealing apparatus using an oven for heattreating astrip ofan amorphous material 30 to produce a nanocrystallized magnetic alloy of low permeability having sufficientWO 2011/060546 15 PCT/CA2010/001844

reduced brittlenessto carry outthe rolling up ofthe strip to form cores without risk of breaking. The annealing process is carried out by forwarding the ribbon through a tunnel furnace in a flat position at afeeding rate greater or equal to 10 em/sec and under a longitudinal tensile stress. Such heat treatment is intended for nanocrystallizing an amorphous alloy which is not sought for when the annealed amorphous ribbon must preserve its amorphous state once annealed. Also, no details are disclosed on heating rates and no references are made aboutthe cooling stage asthe ribbon is simplycollected on atake-up mandrel.
10 Ifan in-line annealing apparatuswas capable ofannealing an iron-based amorphous alloy ribbon in a curved shape and to preserve its ductilitythen, the outputted ribbon could be efficiently rolled up to form a circularcore around the coils ofatransformer kernel such as the one disclosed by Allan et al. Using such an in-line annealing treatmentwould also avoid all the numerous discontinuous steps involved in making the core when using the furnace annealing method. However, this in-line annealing treatment must operate at a cost-effective ribbon feeding rate and the ribbon must acquire acceptable magnetic properties once the ribbon is rolled up to form a core. Even without considering the magnetic properties and the degree of ductility for all the in-line curved annealed amorphous ribbons ofthe above prior art documents, at 20 annealing feeding rates in the 1 to 10 em/sec range as mainly reported, a 22 em wide and 25 IJm thick ribbon (which is the widest size generally available for making conventional transformer cores) would be processed at a mass rate of 1.4 to 14 kg/hr (using the 7.2 g/cm3 material density of the Metglas 2605SA1 alloy). An average core size in a distribution transformer rated between 25 to 167 kVAweighs around 135 kg. At a mass rate of 1.4to 14 kg/hr, this will take over 10 to 100 hours to in-line anneal the ribbon ofasingletransformercore. Thisfeeding rate range isfar too slow ifone wants to renderthis process profitable. Too many annealing setups,

, labour and floor space would be required which increase costs. In order to be profitable, the ribbon feeding rate for a newly developed in-line annealing process 30 must be significantly increased. Doing the treatment at a lower cost within an hour,WO 2011/060546 16 PCT/CA2010/001844

which becomes more reasonable, requires afeeding rate above 1 m/sec, 10to 100 times faster than the feeding rates reported above. To go beyond this rate, the heating and cooling temperature rates compared to those reported in the above methods must be greatly increased, and the annealing time must be shortened by further increasing thetreatmenttemperature. Performing annealing treatments in very short times on an amorphous ribbon have widely been reported in several scientific papers. Many experiments conducted on a ribbon segment have shown thatthe annealing time could be made much shorter. In 10 these experiments, a ribbon specimen was generally placed between two electrodes, making contact at both ends, so that a high current pulse could be passed through the specimen using, for example, a discharge capacitor. Optionally, the experiment could be conducted in a liquid coolantfor a quickercooling. Using a suitable currentdensity, very high heating rates can be obtained and, iffollowed with a rapid cooling, the annealing time can be reduced to afraction ofasecond with the ribbon becoming less brittle than after conventional furnace annealing. Such experiment and results were reported by Kulik et al. in "Influence of Flash Annealing on the Magnetic Properties of a Co-based Alloy Glass", International Journal of Rapid Solidification, 1989, Vol. 4, 287-296, and by Matyja et al. in "Rapid heating of 20 alloy glasses", Philosophical Magazine B, 1990, Vol. 61, No.4, 701-713. These experiments use higher heating and cooling rates than those reported in the above prior art documents. However, the experiments were conducted on immobilized ribbon segments. Applying this method for continuously in-line annealing a forwarding ribbon is impracticable.
None ofthe priorart methods known totheApplicantteach awayto efficiently in-line anneal in a curved shape an iron-based amorphous alloy ribbon forwarded at a feeding rate greater than 1 m/sec and, none ofthem disclose circular cores made with said annealed ribbon which exhibit acceptable core loss and exciting power 30 comparable to cores produced with conventional furnace field annealing and whichWO 2011/060546 

### 17 PCT/CA2010/001844

have a 8

### ao greaterthan about 1.3Tesla and a ratio 8ao /8satgreaterthan 0.80 while remaining ductileforallowing efficient rolling-up-after-annealing.
SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide methods and apparatusto overcome at leastone drawbackofthe priorart. According to the present invention, there is provided a method for treating an 10 amorphous alloy ribbon, comprising steps of: a) feeding forward, tensioning and guiding the amorphous alloy ribbon along a path atapresetfeeding rate; b) heating the amorphous alloy ribbon at a point along said path at a rate greaterthan 103 °C/secto atemperatureto initiate athermal treatment; c) cooling the amorphous alloy ribbon at a rate greaterthan 103 °C/sec until the thermal treatmentends; d) applying aseries ofmechanical constraints on the ribbon during said thermal treatment until the amorphous alloy ribbon adopts a specific shape at rest aftersaid thermal treatment; and 20 e) cooling the amorphous alloy ribbon at a rate to preserve said specific shape, aftersaid thermal treatment. Preferably, according to one preferred embodiment of the present invention, the thermal treatment is performed to maintain an amorphous state ofthe ribbon. Preferably, according to another preferred embodiment ofthe present invention, the thermal treatment is performed to initiate crystallisation of the amorphous alloy ribbon.WO 2011/060546



### 18 PCT/CA2010/001844

Preferably, according to another preferred embodiment ofthe present invention, the thermal treatment is performed to obtain partial crystallisation ofthe amorphous alloy ribbon. Preferably, according to another preferred embodiment ofthe present invention, the thermal treatment is performed to obtain full crystallisation of the amorphous alloy ribbon. Preferably, the presetfeeding rate is greaterthan 1 m/sec. 10 Preferably, in step b), the heating is done ata rate greaterthan 104 DC persecond. Preferably, in step c), the cooling is done at a rate greaterthan 104 DC persecond. Preferably, according to one preferred embodiment of the present invention, the thermal treatment is performed during aperiod oftimethat is lessthan one second. Preferably, according to another preferred embodiment ofthe present invention, the thermal treatment is performed during aperiod oftimethat is lessthan one tenth ofa 20 second. Preferably, step e) cools the amorphous alloy ribbon to a handling temperature above a temperature threshold Tdb0 to which a complete ductility ofthe amorphous alloy ribbon is obtained. Preferably, the handling temperature is above ambienttemperature and belowsaid temperature to initiatethe thermal treatment. Preferably, in step b) the amorphous alloy ribbon is in contact with at least one first 30 cylinder having a first cylindrical surface located along said path; step b) furtherWO 2011/060546 

### 19 PCT/CA2010/001844

comprises a step oftensioning the amorphous alloy ribbon with respect to the first cylindrical surfaceto obtain afirst staticcontact between the amorphous alloy ribbon and the first cylindrical surface, the first static contact stretching over afirst contact angle around the first cylindrical surface; step b) further comprises a step of maintaining said first cylindrical surface at a temperature greater or equal to said temperature to initiatethe thermal treatment; in step c) the amorphous alloy ribbon is in contact with at least one second cylinder having a second cylindrical surface located along said path; step c) further comprises a step of tensioning the amorphous alloy ribbon with respect to the second cylindrical surface to obtain a 10 second staticcontact between the amorphous alloy ribbon and the second cylindrical surface, the second staticcontact stretching overasecond contact angle around the second cylindrical surface; and step c) further comprises a step of maintaining said second cylindrical surface at a temperature lower than said temperature to initiate thethermal treatment. Preferably, in step d) the amorphous alloy ribbon is in contactwith at least one third cylinder having a third cylindrical surface located along said path; step d) further comprises a step oftensioning the amorphous alloy ribbon with respect to the third cylindrical surface to obtain a third static contact between the amorphous alloy 20 ribbon and the third cylindrical surface, the third static contact stretching overathird contact angle around the third cylindrical surface; and step d) further comprises a step of maintaining said third cylindrical surface at said temperature to initiate the thermal treatment. Preferably, the step of tensioning the amorphous alloy ribbon with respect to the cylindrical surfaces is done atatension in the range of25to 200 MPa.
More preferably, the step of tensioning the amorphous alloy ribbon with respect to the cylindrical surfaces is done atatension in the range of50to 100 MPa. 

### 30WO 2011/060546 20 PCT/CA2010/001844

Preferably, the step oftensioning the amorphous alloy ribbon is done to favour the developmentofa magneticanisotropy in the ribbon. Preferably, the amorphous alloy ribbon is in contact with at least one guide roller proximate a selected one of the first, second or third cylinders, said guide roller having a radius that is smaller than the selected cylinder and being positioned proximate both an initial contact point and a final contact point between the ribbon and the selected cylinderto maximize said contact angle ofsaid selected cylinder.
10 Preferably, in step d) the specific shape is curved and the method further comprises an additional step of: 

### f) rolling up a specific amount of the amorphous alloy ribbon onto a mandrel to form a core having an inner radius and an outer radius, wherein said specific shape has a radius ofcurvature selected between said inner radius and said outer radius. Preferably, in step d) the specific shape is flat and the method further comprises an additional step of: 

### f) cutting and stacking segments ofthe amorphous alloy ribbon.
20 Preferably, in step d) the mechanical constraints change to vary a radius of curvature ofthe specificshape ofthe amorphous alloy ribbon along a length thereof, and the method furthercomprises an additional step of: 

### f) rolling up said length ofthe amorphous alloy ribbon onto a mandrel to form a core. Preferably, the method furthercomprises an additional step before step

### f) of: i) coating at least one side of the amorphous alloy ribbon with a dielectric material.
30 Preferably, the dielectric material is an organicdielectric material.WO 2011/060546 

### 21 PCT/CA2010/001844

Preferably, in step i) coating is performed by means ofelectrodepositing. Preferably, step i) further comprises steps of applying a voltage on the amorphous alloy ribbon and feed forwarding the ribbon in an emulsion oforganic polymers and de-ionized waterforaperiod oftime. Preferably, the method furthercomprises an additional step before step f) of: i) coating at leastone side ofthe amorphous alloy ribbon with a binder. 

### 10 Preferably, atension is increased or reduced along the path ofthe amorphous alloy ribbon byatensioning apparatus, said tensioning apparatus comprising: at leastone motorhaving ashaft; a circular device coupled to the shaft of the motor, said circular device having a surface making a static contactwith the ribbon over an angle, the surface having astaticfriction coefficientwith respecttothe ribbon; and - a controllerfor controlling torque of said motor shaft to increase or reduce a tensile stress in the amorphous ribbon.
20 Preferably, the tensioning apparatus is located along said path to increase the tensile stress in the ribbon beforethermal treatment is initiated. Preferably, the tensioning apparatus is located along said path to reduce the tensile stress aftersaid thermal treatment. Preferably, the tensioning apparatus is located along said path for controlling the tensile stress in the ribbon during said thermal treatment. Preferably, the ribbon being fed along the path is delivered to atarget position on a 30 structure byaguiding apparatus, said guiding apparatus comprising:WO 2011/060546 

### 22 PCT/CA2010/001844

- abody; - a guide roller mounted on the body, having a flat peripheral surface lined with lateral guides for supporting and guiding the ribbon, the guide roller having a receiving section for receiving the ribbon and a delivering section for delivering the ribbon atthetarget position; and - a pivotfor pivotably mounting the bodyto the structure, the pivot having a pivot axis tangentially aligned with the delivering section of the roller; in operation, the body pivots with respect to the structure by means ofthe pivot so that the receiving section of the roller receives the ribbon and accommodates translations thereof to 10 delivervia said delivering section the ribbon atthetarget position. Preferably, in step e) the amorphous alloy ribbon is in contact with a plurality of spaced apart cooling cylinders each having a cooling cylindrical surface located along said path; step e) further comprises a step oftensioning the amorphous alloy ribbon with respect to the cooling cylindrical surfaces to obtain a cooling static contact between the moving amorphous alloy ribbon and the cooling cylindrical surfaces, the cooling static contact stretching over respective contact angles around the cooling cylindrical surfaces; and step e) further comprises a step of maintaining said cooling cylindrical surfaces at a temperature lower than said temperature to 20 initiatethethermal treatment. According to the present invention, there is also provided an iron-based amorphous alloy cast as a ribbon, heat-treated by in-line annealing at a temperature without reaching onset crystallization with heating and cooling at temperature rates greater than 103°C/sec, preferablygreaterthan 104°C/sec. Preferably, when said ribbon is stacked or rolled up to form a core, its 

### Bao/Bao is greaterthan 0.80 afterannealing.WO 2011/060546 23 PCT/CA2010/001844

Preferably, when said ribbon is stacked or rolled up to form a core, its BaD is greater than about 1.3Tesla afterannealing. Preferably, under this treatment, the ribbon is ductile at normal room temperature and completely ductile above atemperature greaterthan normal room temperature According to the present invention, there is also provided an iron-based amorphous alloy cast as a ribbon comprising a nominal chemical composition FeaoB11Sig, numbers being in atomic percent, with incidental impurities, heat-treated by in-line 10 annealing at a temperature above 450°C without reaching onset crystallization with heating and cooling attemperature rates greaterthan 103°C/sec. According to the present invention, there is also provided an iron-based amorphous alloy, comprising a nominal chemical composition FeaBbSicCd where 80<a<84, 8<b<18, 0<c:55 and 0<d:53, numbers being in atomic percent, with incidental impurities, heat-treated by in-line annealing at a temperature above 425°C without reaching onset crystallization with heating and cooling at temperature rates greater than 103DC/sec.
20 Preferably, under this treatment, the ribbon is ductile at normal room temperature and completelyductile at atemperature greaterthan 80°C. Preferably, the iron-based amorphous alloy comprises a nominal chemical composition Fe81.8B15.8Si2.1Co.3, numbers being in atomic percent, with incidental impurities. According to the present invention, there is also provided a heat exchange system forexchanging heatwith an article comprising: -a supportstructure; 30 -a heatexchanger ring elementcapable ofbeing heated;WO 2011/060546 

### 24 PCT/CA2010/001844

-a heat diffuser ring element having an outersurface to be in contactwith said article, said heat diffuser ring element having an inner surface in contact with said heatexchangerring element; and -a frame structure supporting said heat exchanger ring element and said heat diffuser ring element, said frame structure being rotatably mounted on the supportstructure. Preferably, the heat exchanger ring element is a resistive element capable of being in sliding rotatable contactwith an electrical powersource. 10 Preferably, according to another embodiment of the invention, the heat exchanger ring element is a resistive element further comprising an antenna for heating by magnetic induction the heatexchanger ring element. Preferably, the heatexchange system furthercomprises aslotted structure integrally formed with the heat exchanger ring element and laterally surrounding said heat exchanger ring element, the slotted structure having slots extending transversallyto the heatexchanger ring element.
20 Preferably, the heat exchanger ring element is made ofstainless steel and the heat diffuser ring element is made of copper and mounted by electrodeposition on the heatexchanger ring element. According to the present invention, there is also provided a system for treating an amorphous alloy ribbon, comprising: -a moving device for feeding forward, tensioning and guiding the amorphous alloy ribbon along a path ata presetfeeding rate; -a heating system for heating the amorphous alloy ribbon at a point along said path at a rate greater than 103 DC/sec to a temperature to initiate a thermal 30 treatment;WO 2011/060546 

### 25 PCT/CA2010/001844

-a first cooling system cooling the amorphous alloy ribbon at an initial rate greaterthan 103 °C/sec until the thermal treatment ends; -a mechanical constraint application device for applying a series of mechanical constraints on the ribbon during said thermal treatment until the amorphous alloy ribbon adopts aspecificshape at restaftersaid thermal treatment; and -a second cooling system for cooling the amorphous alloy ribbon at a rate to preserve said specificshape, aftersaid thermal treatment. Preferably, the presetfeeding rate is greaterthan 1 m/sec. 10 Preferably, the heating system heats ata rate greaterthan 104oC persecond. Preferably, thefirst cooling system cools at a rate greaterthan 104oC persecond. Preferably, the second cooling system cools the amorphous alloy ribbon to a handling temperature above a temperature threshold Tdb°that is sufficient to obtain complete ductilityofthe amorphous alloy ribbon. Preferably, the heating system comprises at least one first cylinder in contact with 20 the amorphous alloy ribbon, said at least one first cylinder having a first cylindrical surface located along said path, the system further comprising a first tensioning apparatus for tensioning the amorphous alloy ribbon with respect to the first cylindrical surface to obtain afirst staticcontact between the amorphous alloy ribbon and the first cylindrical surface, the first static contact stretching over a first contact angle around the first cylindrical surface, a temperature of said first cylindrical surface being maintained at a temperature greater or equal to said temperature to initiate the thermal treatment, the first cooling system comprises at least one second cylinder in contactwith the amorphous alloy ribbon, said at leastone second cylinder having a second cylindrical surface located along said path, the system further 30 comprising a second tensioning apparatusfortensioning the amorphous alloy ribbonWO 2011/060546 

### 26 PCT/CA2010/001844

with respect to the second cylindrical surface to obtain a second static contact between the amorphous alloy ribbon and the second cylindrical surface, the second static contact stretching over a second contact angle around the second cylindrical surface, a temperature of said second cylindrical surface being maintained at a temperature lowerthan said temperatureto initiatethethermal treatment. Preferably, the mechanical constraint application device comprises in contact with the amorphous alloy ribbon, said at least one third cylinder having athird cylindrical surface located along said path, the system further comprising a third tensioning 10 device fortensioning the amorphous alloy ribbon with respect to the third cylindrical surface to obtain athird static contact between the amorphous alloy ribbon and the third cylindrical surface, the third static contact stretching over athird contact angle around the third cylindrical surface, a temperature of said third cylindrical surface being maintained atsaid temperatureto initiatethethermal treatment. Preferably, the tensioning apparatuses tension the amorphous alloy ribbon with respecttothe cylindrical surfaces atatension in the range of25to 200 MPa.
More preferably, thetensioning apparatusestension the amorphous alloy ribbon with 20 respecttothe cylindrical surfaces atatension in the range of50to 100 MPa. Preferably, wherein the tensioning apparatuses tension the amorphous alloy ribbon tofavourthe developmentofa magneticanisotropy in the ribbon. Preferably, the system further comprises at least one guide roller to which the amorphous alloy ribbon is in contact, proximate aselected one ofthe first, second or third cylinders, said guide roller having a radius that is smaller than the one ofthe selected cylinders and being positioned proximate both an initial contact point and a final contact point between the ribbon and the selected cylinder to maximize said 30 contact angle ofsaid selected cylinder.WO 2011/060546 

### 27 PCT/CA2010/001844

Preferably, according to one embodimentofthe present invention, the system further comprises a mandrel onto which a specific amount ofthe amorphous alloy ribbon is rolled up, said mandrel having an inner radius and an outer radius, said specific shape having a radius of curvature selected between said inner radius and said outer radius. Preferably, according to another embodiment of the present invention, the system further comprises a cutter and stacking device for cutting and stacking segments of 10 the amorphous alloy ribbon. Preferably, according to one embodiment of the present invention, the mechanical constraint application device apply constraints to vary a radius of curvature of the specificshape ofthe amorphous alloy ribbon along a length thereof, and the system further comprises a mandrel onto which a specific amount of the amorphous alloy ribbon is rolled up. Preferably, the system further comprises a coating system for coating at least one side ofthe amorphous alloy ribbon with adielectric material. 

### 20 Preferably, the dielectric material is an organicdielectric material. Preferably, the coating system is an electrodepositing system. Preferably, the system further comprises avoltage application device for applying a voltage on the amorphous alloy ribbon, and a bath system comprising an emulsion oforganic polymers and de-ionized waterthrough which the ribbon is fed forward for aperiod oftime.WO 2011/060546 

### 28 PCT/CA2010/001844

Preferably, the system further comprises a binder application system for coating at leastone side ofthe amorphous alloy ribbon with abinder. Preferably, the system further comprises a tensioning apparatus for increasing or reducing a tension in the amorphous alloy ribbon along the path, said tensioning apparatus comprising: at leastone motorhaving ashaft; - a circular coupled to the shaft of the motor, said circular device having a surface making a static contact with the ribbon over an angle, the surface 10 having astaticfriction coefficientwith respecttothe ribbon; and - a controllerfor controlling torque of said motor shaft to increase or reduce a tensile stress in the amorphous ribbon. Preferably, the second cooling system comprises a plurality ofspaced apart cooling cylinders in contact with the amorphous alloy ribbon, said spaced apart cooling cylinders each having a cooling cylindrical surface located along said path, the system further comprising a tensioning system for tensioning the amorphous alloy ribbon with respect to the cooling cylindrical surfaces to obtain a cooling static contact between the moving amorphous alloy ribbon and the cooling cylindrical 20 surfaces, the cooling static contact stretching over respective contact angles around the cooling cylindrical surfaces, a temperature of said cooling cylindrical surfaces being maintained atatemperature lowerthan said temperatureto initiatethe thermal treatment.
A non-restrictive description of a preferred embodiment ofthe invention will now be given with referencetothe appended drawings.WO 2011/060546 

### 29 BRIEF DESCRIPTION OF THE DRAWINGS PCT/CA2010/001844

Figure 1 is a schematic view of a system for in-line annealing an amorphous alloy ribbon in a curved shape by forwarding the ribbon over a hot and then over a cold roller, in accordancewith a preferred embodimentofthe present invention; Figure 2 is a schematicview ofthe system shown in Figure 1 with the addition ofa ribbon feeding reel and atake-up mandrel;
10 Figures 3a and 3b are schematic views of the system shown in Figure 1 with the addition ofasmall guide rollerfor increasing contact angle overthe rollers; Figure 4a is a schematicview ofthe system shown in Figure 1 with the addition ofa hot rollerforpre-heating the ribbon; Figure 4b is a schematic view ofthe system shown in Figure 1 with the addition of two hot rollersforpre-heating the ribbon; Figure 5 is a schematic view ofthe system shown in Figure 4b with the addition of 20 three cold rollers forfurthercooling ofthe ribbon; Figure 6a is a schematicview ofthe system shown in Figure 1 with the addition ofa hot rollerforannealing the alloy ribbon atvariable curvatures; Figure 6b is a schematicview ofthe system shown in Figure 1 with the addition ofa hot rollerforannealing the alloy ribbon in aflat bend form; Figure 7a is a graph showing the temperature profile of the ribbon while moving along a travelling path within the system shown in Figure 24 when not using pre30 heating;WO 2011/060546 30 PCT/CA2010/001844

Figure 7b is a graph showing the temperature profile of the ribbon while moving along atravelling path within the system shown in Figure 24 when using pre-heating; Figure 7c is a graph showing the temperature profile ofthe ribbon while passing over the cold rollers shown in Figure 5; Figure 8 is a graph showing the temperature profile ofthe ribbon while moving along a travelling path within the system shown in Figure 24 when cooling the ribbon to a 10 temperature abovethe ductileto brittlethreshold; Figure 9 is a perspective view of inner and outer cladding rings of a hot roller according to a preferred embodimentofthe present invention; Figure 10 is a perspective view of inner and outer cladding rings of a hot roller comprising an induction antenna according to a preferred embodimentofthe present invention; Figure 11 is a perspective view ofa hot roller construction according to a preferred 20 embodimentofthe present invention; Figure 12 is a perspective view ofa hot rollershown in Figure 11 with aflange and a hollowshaft; Figure 13 is a side cross-section view and a detailed view respectively of the hot rolleraccording shown in Figure 12 mounted on asupporting member; Figure 14 is a side cross-section view of a cold roller according to a preferred embodimentofthe present invention; 30WO 2011/060546 

### 31 PCT/CA2010/001844

Figure 15a is aside cross-section viewofacold rolleraccording to anotherpreferred embodiment ofthe present invention; Figure 15b is a perspective view of some elements comprised in the hollow portion ofthe cold rollershown in Figure 15a; Figure 16 is aschematicview ofasystem to delivera ribbon at a precise location on aguiding rolleraccording to a preferred embodiment ofthe present invention;
10 Figure 17 is a perspective view of a system to deliver a ribbon at a precise location on a guiding roller according to another preferred embodiment of the present invention; Figure 18a is aschematic illustration ofa ribbon passing overa capstan wheel; Figure 18b is a plotted curve of the tensile force vs. angular position applied by a capstan wheel on a ribbon; Figures 19a and 19b are a front view and a perspective view of a capstan drive 20 according to a preferred embodimentofthe present invention; Figures 20a and 20b are a front view and a perspective view offour capstan drives according to anotherpreferred embodimentofthe present invention; Figure 21 is a schematic view of a ribbon tensioning apparatus with two capstan drives, according to apreferred embodimentofthe present invention; Figure 22 is a schematic view of a ribbon tensioning apparatus with a plurality of capstan drives, according to anotherpreferred embodiment ofthe present invention; 

### 30WO 2011/060546 32 PCT/CA2010/001844

Figure 23 is a schematic view of an in-line annealing apparatus comprising: a system for in-line annealing an amorphous alloy ribbon in a curved shape; a ribbon tensioning apparatus, a system to delivera ribbon at a precise location on aguiding roller; afeeding reel; and atake-up mandrel according to a preferred embodimentof the present invention; Figure 24 is a schematic view of a system for a system for in-line annealing an amorphous alloy ribbon in a curved shape according to another preferred embodimentofthe present invention; 

### 10 PREFERRED EMBODIMENTS OF THE PRESENT INVENTION
Different preferred objects ofthe present invention will now be presented.
It is an object of the present invention to provide an in-line annealing method and apparatus for heat treating an amorphous alloy ribbon at high ribbon heating and cooling rates.
It is another object ofthe present invention to provide an in-line annealing method 20 and apparatusfor heattreating an amorphous alloy ribbon to adopt aspecific shape at restafterthethermal treatment. Preferably, is another object ofthe present invention to provide a curved annealed and ductile iron-based amorphous alloy ribbon that can be used to manufacture circularmagneticcores at lowcost. Preferably, it is anotherobject ofthe present invention to provide a low cost process for in-line annealing an amorphous alloy ribbon.WO 2011/060546 33 PCT/CA2010/001844

Preferably, it is another object ofthe present invention to provide a process for inline annealing an amorphous alloy ribbon which is compact. Preferably, it is another object ofthe present invention to provide a process for inline annealing an amorphous alloy ribbon which operates at high ribbon feeding rates. Preferably, it is anotherobjectofthe present invention to provide aflat annealed and ductile iron-based amorphous alloy ribbon that can be used to manufacture stacked 10 magneticcores at lowcost. Preferably, it is anotherobjectofthe present invention to provide an in-line annealed an iron-based amorphous alloy ribbon which exhibit acceptable magnetic properties for manufacturing cores for distribution transformers, HIF, pulse power cores, and other items.
The present invention is based on the idea that it is not essential to heat, treat and cool aferromagnetic amorphous alloy ribbon in the same shape as itwill have after treatment in orderto get a ribbon to have acceptable magnetic properties for making 20 distribution transformers, HIF, pulse power cores, and other items. It is believed that an amorphous alloy ribbon can be in-line annealed with the ribbon following a series ofdifferent predetermined configurations while being forwarded along the treatment. This is done by controlling the flow sequence occurring in the alloy at the treatment temperature to ensure its progression towards a structural state where most ofthe residual stresses and applied bending stresses will be alleviated when the ribbon will be bent close to a final shape after treatment. With the apparatus of the present invention, an amorphous alloy ribbon is in-line annealing to adopt a desired final shape after treatment. In the present invention, the treatment temperature must be sufficiently high and must last sufficient long so that the obtained reduced viscosity 30 will allow sufficient flowto occur along the series of imposed configurations in orderWO 2011/060546 34 PCT/CA2010/001844

to affect the resulting final shape after treatment. With the present invention, it is possible to provide a heattransfer rate much higherthan the ones obtained with the above methods of the prior art. Preferably, a high heat transfer rate is provided by using a prolonged direct static contact between one ofthe two side surfaces ofthe forwarded ribbon and along a significant peripheral portion ofathermally conductive circular rotating body (a static contact is referred in this document to a non-slipping direct mechanical contact between two surfaces). Using higher heat transfer rates for heating and cooling will improve the ribbon temperature rising orfalling rate. With the present invention, it is possible to heat or cool a 20 to 30**~m** thick metal ribbon 10 at a temperature rising orfalling rate greaterthan 103 C/seconds, and preferably, in certain cases, even greaterthan 104 C/seconds. With the present invention, cooling is subdivided in two consecutive stages: There is afirst stage cooling operating at a high temperature falling rate, which will serve to quickly bring the ribbon temperature sufficiently below the treatment temperature, in order to sufficiently slow flow and structural relaxation and therefore stopping the thermal treatment. The first stage is followed by second stage cooling at a sufficient temperature falling rate which will serve to bring down the ribbon temperature to a point where the ribbon structural state at the end of the thermal treatment will be preserved. Preferably, after first stage cooling, flow and structural relaxation are slowed to a point where no 20 significant structural change will further occurto the alloy due to the ribbon handling occurring in the second stage cooling. With the present invention, according to preferred embodiments, it is possible to limit structural relaxation in the in-line annealing treatment to get a ductile ribbon. With the present invention, according to preferred embodiments, it is possible to in-line anneal an iron-based amorphous alloy ribbon at a treatment temperature above conventional furnace annealing temperatures without reaching onset crystallization. With the present invention, it is possible to use stress annealing in the production of amorphous alloy cores usable to manufacture cores fordistribution transformers, HIF, pulse powercores, and other items. With the present invention, according to preferred embodiments, it is possible 30 to continuously in-line anneal a forwarding ribbon in a period less than a second,WO 2011/060546 '35 PCT/CA2010/001844

preferably lessthan one tenth ofasecond, to limitstructural relaxation and therefore to get a ductile ribbon. With the present invention, according to preferred embodiments, it is also possible to in-line anneal an amorphous ferromagnetic alloy ribbon at feeding rates greater than 1 m/sec, even at feeding rates greater than about 5 m/sec, even in the 101 m/sec rate range, therefore allowing a high mass production rate of annealed ribbon material for making rolling-up-after-annealing cores. With the present invention, according to preferred embodiments, the size of the in-line annealing apparatus is small and requires minimal floor space, which significantly contributes to reduce costs. With the present invention, according to 10 preferred embodiments, it is possibleto produce rolling-up-after-annealing cores that exhibit lower core loss compared to conventional annealing-after-rolling cores. With the present invention, according to preferred embodiments, it is possible to produce rolling-up-after-annealing cores that exhibit a B

### ao greaterthan about 1.3 Tesla. With the present invention, according to preferred embodiments, it is possible to produce rolling-up-after-annealing cores that exhibit a 

### Bao/Bsat greater than 0.80. With the present invention, according to preferred embodiments, it is possible to in-line anneal an iron-based amorphous alloy ribbon which is cuttable after treatment, for allowing easy rolling-up-after-annealing. With the present invention, according to preferred embodiments, it is possible to in-line anneal an iron-based amorphous 20 alloy ribbon which is foldable on at least one side aftertreatment. With the present invention, according to preferred embodiments, it is possible to in-line anneal an iron-based amorphous alloy which remains ductile aftertreatment. With the present invention, according to preferred embodiments, it is possible to in-line anneal an iron-based amorphous alloy which can be handled in a complete ductile state after treatment. With the present invention, according to preferred embodiments, it is possible to in-line anneal an iron-based amorphous alloy in a completely ductile state during the whole treatment process to minimize risk of breakage. With the present invention, according to preferred embodiments, it is possible to in-line anneal an iron-based amorphous alloy ribbon where Tdb0 remains belowthe normal 30 room temperature aftertreatment. With the present invention, according to preferredWO 2011/060546 36 PCT/CA2010/001844

embodiments, it is possible to in-line anneal an iron-based amorphous alloy ribbon which can be punch, cutortorn, aftertreatment.
In the present invention, according to preferred embodiments, there is provided an iron-based amorphous alloy, when cast in a ribbon, such an amorphous alloy heattreated by in-line annealing at temperatures without reaching onset crystallization with heating and cooling at temperature rates greater than 103 °C/sec, preferably greaterthan 104 °C/sec, has a Bso/Bsa! greaterthan 0.80 when the ribbon is stacked or rolled up to form a core. In addition, such an amorphous alloy is ductile at normal 10 room temperature. In addition, such an amorphous alloy is completely ductile above atemperature slightlygreaterthan normal room temperature.
In the present invention, according to preferred embodiments, there is provided an iron-based amorphous alloy having a nominal chemical composition FesoB11Sig, numbers being in atomic percent, with incidental impurities. When cast in a ribbon, such an amorphous alloy heat-treated by in-line annealing at temperatures above 450°C without reaching onset crystallization with heating and cooling attemperature rates greater than 103 °C/sec, preferably greater than 104 °C/sec, has a Bso/Bsa! greaterthan 0.80 when the ribbon is stacked or rolled up to form a core. In addition, 20 such an amorphous alloy is ductile at normal room temperature. In addition, such an amorphous alloy is completely ductile above a temperature slightly greater than normal room temperature, preferably above 100°C. In addition, such an amorphous alloy in a core has a Bso greater than about 1.3 Tesla. In addition, such an amorphous alloy in a core has a core loss lower than 0.25 W/kg at 60 Hz at a magnetic induction of 1.3Tesla.
In the present invention, according to preferred embodiments, there is provided an iron-based amorphous alloy having a chemical composition FeaBbSicCd where 80<a<84, 8<b<18, 0<cs;5 and 0<ds;3, numbers being in atomic percent, with 30 incidental impurities. When cast in a ribbon, such an amorphous alloy heat-treatedWO 2011/060546 

### 37 PCT/CA2010/001844

by in-line annealing at temperatures above 425°C without reaching onset crystallization with heating and cooling attemperature rates greaterthan 103°C/sec, preferably greaterthan 104 °C/sec, has a Bso/Bsat greaterthan 0.80 when the ribbon is stacked or rolled upto form a core. In addition, such an amorphous alloy is ductile at normal room temperature. In addition, such an amorphous alloy is completely ductile above a temperature slightly greater than normal room temperature, preferably above 80°C. In addition, such an amorphous alloy in the core has a Bso greaterthan about 1.3 Tesla, even greaterthan about 1.4 Tesla, even greaterthan about 1.5 Tesla. In addition, such an amorphous alloy in the core has a core loss 10 lowerthan 0.25W/kg at60 Hz at a magnetic induction of 1.5Tesla.
In the present invention, according to preferred embodiments, there is provided an iron-based amorphous alloy having a nominal chemical composition Fes1.8B15.sSi2.1Co.3, numbers being in atomicpercent, with incidental impurities. When cast in a ribbon, such an amorphous alloy heat-treated by in-line annealing at temperatures above 425°C without reaching onset crystallization with heating and cooling at temperature rates greater than 103°C/sec, preferably greater than 104 DC/sec, has a Bso/Bsat greater than 0.80, preferably greater than 0.90, when the ribbon is stacked or rolled up to form a core. In addition, such an amorphous alloy is 20 ductile at normal room temperature. In addition, such an amorphous alloy is completely ductile above a temperature slightly greater than normal room temperature, preferably above 80oC. In addition, such an amorphous alloy in the core has a Bso greaterthan about 1.3Tesla, even greaterthan about 1.4Tesla, even greaterthan about 1.5Tesla. In addition, such an amorphous alloy in the core has a core loss lowerthan 0.25W/kg at60 Hz at amagnetic induction of 1.5Tesla. Referring to Figure 1, there is shown an apparatus for in-line annealing an amorphous alloy ribbon comprising: a hot roller 1 having an outer radius r1; a cold roller 2 having a smaller outer radius r2 and rotating in parallel and at a selected 30 distance d from roller 1. The hot and cold rollers outer surfaces are constituted ofaWO 2011/060546 

### 38 PCT/CA2010/001844

material having athermal conductivity and athermal inertia. The hot and cold rollers comprise a heat source and/or heat sink for controlling the heat flux entering in or exiting out from each roller. The flow of heat between the heat source and/or heat sink and a roller can be performed using a heat transferfluid, or gas, circulating in contact with the thermally conductive inner surface of a sealed hollow roller and passing through the rollervia entry and exit holes located in the center ofthe shaft. For heatflux entering in a roller, the heattransferfluid, orgas, can be substituted by aflame from a burneror by an electrical heating element in contactwith the thermal conductive inner surface of a hollow roller. The electrical heating element can be 10 connected to an electrical power supply via sliding contacts provided on the roller shaft, orpreferably, by using afixed High frequency (HF) magnetic induction heating antenna located within the hollow portion ofthe roller and in close proximity to the inner roller surface which has an electrical conductivity, the HF magnetic induction antenna being connected to an HF electrical source through an opening in the roller shaft.
Athin amorphous alloy ribbon isfed atentry point 3at agiven ribbon feeding rate, a temperature Tin

## ° and under a first mechanical tensile stress 81 applied along the ribbon longitudinal axis. The ribbon is then guided through a selected path along 20 which itwill be subjected to aseries ofphysical deformations and thermal treatments before leaving at exit point 7 at the same feeding rate, at a temperature ToutO and underasecond applied mechanical tensile stress 82. Preferably, the ribbon entering at point 3shows little structural change compared to its as-cast state. The treatment sequence can be best described by selecting a segment of the ribbon located at entry point 3and to followthe series ofthermal and structural changes while moving along the travelled path. From point 3 and moving along, the ribbon first makes a static contact at point 4 on the outersurface of hot roller 1 where it bends to radius r1. From this point, the ribbon starts to heat up at a high temperature rising rate and is kept in contact with hot roller 1 for a given rotation angle 81, up to point 5. While 30 rotating along with hot roller 1 outer surface, the ribbon temperature goes up to aWO 2011/060546 

### 39 PCT/CA2010/001844

treatment temperature below or equal to the hot roller 1 outer surface temperature. At point 5, the hot ribbon breaks contactwith hot roller 1 and goes through in aflat configuration and atthe treatmenttemperature to point 6 located at atravel distance 

### dfrom point 5to make a second static contactwith the outersurface of cold roller2 parallel to roller 1 and, where it bends on the same side again to radius r2. From this point, the ribbon starts to cool down at a high temperature falling rate. The ribbon is kept in contact with cold roller 2 for a given rotating angle 82 up to point 8. While rotating along on cold roller 2, the ribbon temperature goes down to a temperature ToutOabove orequal to the cold roller2 outersurface temperature. After leaving cold 10 roller2, the ribbon is eithertaken-up on a mandrel and slowly cools down to normal room temperature or, is moved awayforfurther cooling (forexample: additional cold rollers) orprocessing before being rolled on atake-up mandrel.
The setup apparatus of Figure 1 is best suited to continuously stress relieve a forwarding thin amorphous alloy ribbon to adopt a curved shape. Normally, the amorphous alloy ribbon will have athickness upto 50 IJm, moretypically at about20 to 30 IJm. In the present invention, the post-process natural bending radius r a in a rest position atwhich the ribbon will show maximum alleviated stress is greaterthan radius r2 aftertreatment. In orderto be so, the ribbon temperature must go up to a 20 treatment temperature for a sufficient period of time in order to relieve the residual and applied bending stresses due to increased flow and to the presence ofatensile stress in the ribbon. The controlling oftheflowsequence occurring in the alloyatthe treatmenttemperature is controlled bythe sequence ofbending stresses imposed on the ribbon with rollers rotating in contactwith theforwarded ribbon along the thermal treatment path. During treatment, the ribbon successively changes configuration from being bentto radius r1, then being flat and, being bent again on the same side to radius r2. A portion of the stress relieving is occurring on roller 1 when the treatment temperature is reached. The travel path from point 5 to point 6 on cold roller 2 is done in a flat configuration at the treatment temperature and an added 30 unbending applied stress is getting relieved. Once point 6 reached, stress reliefWO 2011/060546 

### 40 PCT/CA2010/001844

action of the reapplied bending stress imposed at a small radius r2 on the same bending side as on roller 1 is occurring whilethe ribbon'stemperature is still nearthe treatment temperature during the initial portion ofthe first cooling stage. This way, the ribbon will regain a substantially alleviated stress condition when bent close to radius rawhich is greaterthan r2. When leaving the roller at point 8, the first cooling stage is done and the ribbon temperature ToutO has dropped sufficiently below the treatmenttemperature to allowfurther ribbon handling while continuing to cool down in the second cooling stage without provoking further significant detrimental stress relief. As the alloy's viscosity increases with the reciprocal of the temperature by 10 closely following an Arrhenius law, a drop of a few tens of degrees from the treatment temperature is sufficient. Second stage cooling can be done when the ribbon is rolled on the take-up mandrel or preferably, using any additional cooling means such as additional cold rollers, ora cooling jet ofgas, before being taken-up on a mandrel. The resulting natural bending radius ra in a rest position after treatment becomes afunction of ribbon thickness and feeding rate, temperatures of rollers 1 and 2, radius r1 and r2, contacting angles 81 and 82 and distance d. Also, a tensile stress is maintained all along the displacementofthe ribbon during treatment to induce a magnetic anisotropy oriented along or perpendicular to the ribbon longitudinal axis, depending on the alloycomposition. 20 In the apparatus of Figure 1, the highest ribbon feeding rate that can be achieved, while keeping an acceptable annealing treatment, is limited bythe heattransfer rate between a rollerand the ribbon, bythe ribbon thickness, bythe angulardistance (8 x r) of the contact region, and by the roller temperature. The heat transfer rate between a roller and the ribbon is dependent on the contact area between both mating surfaces. Dueto some roughness characteristics ofboth mating surfaces, the contact area is reduced to a fraction which is influenced by the applied contact pressure. The contact area will be improved if some pressure is applied. Also, a reduced viscosity at elevated temperature will improve the contact area under theWO 2011/060546 

### 41 PCT/CA2010/001844

pressuring force. Furthermore, the contact area will improve for amorphous alloy ribbons having a reduced surface roughness. In the shown apparatus, a contact pressure is exerted bythe applied mechanical tensile stress in the forwarded ribbon in orderto stranglethe roller. This strangling force creates acontact pressuring force which is proportional to the tensile stress and inversely proportional to the roller radius. The radius r2 of roller2 being smallerthan radius r1 of roller 1, the ribbon will have a higher contact area on roller 2 at cool down. Also, the temperature rate of change in the ribbon while in contact with a roller evolves closely following a negative exponential decay: _e-x (heating ribbon), or positive exponential decay: e-x 10 (cooling ribbon), as the temperature gap between the ribbon and the roller surface diminishes, as shown in Figure 7a. Preferably, the surface temperature of roller 2 is well belowthe treatmenttemperature totake benefitofthe higherfalling temperature rate occurring atthe initial portion ofthe closely followed positive exponential decay (e-X). The maximum ribbon feeding rate for maintaining the same annealing curvature is achieved when the temperature ToutO has not dropped sufficiently below the treatmenttemperature at point 8to allowfurther ribbon handling while continuing to cool down in the second cooling stage without provoking further significant detrimental stress relief. In this case, thermal treatment is not ended and the first cooling stage must be continued by contacting on a second cold roller 2 in close 20 proximityto the first cold roller2. The resulting final curved shape will be determined byconsidering the effectofthis added rolleron the thermal treatment. Preferably, the annealing process ofthe present invention is carried out to minimize structural relaxation in order to get a ductile ribbon. It is believed that the dependence to the reciprocal of the temperature of the amorphous alloy instantaneous viscosity and rate of viscosity increase with time closely follow an Arrhenius lawfortemperatures belowTgo. At an elevated temperature butstill below TgO, the reduced viscosity will cause flow to increase in response to stress. For an initial applied or residual stress, the effectofflowwill gradually relieve the stresswith 30 time with an associated time constant. In aconstant structure (i.e.: with no structuralWO 2011/060546 

### 42 PCT/CA2010/001844

relaxation), this time constant is exponentially proportional to the reciprocal temperature ofthe alloy. The higherthe temperature, the shorterthe required stress relieftime will be. Furthermore, ifthere is a constant applied stress, there will be a constant flow. However, with structural relaxation also occurring, there will be an increasing resistancetoflowdueto acontinuing increase oftheviscosityasthe alloy atomic structure rearranges towards an equilibrium state. This will stretch the time constant to relieve the stresses which will be irreversible since there has been a structural change in the alloy. Due to the effect ofstructural relaxation, the required time to stress relieve asudden applied stress on an amorphous alloy specimen at a 10 predetermined temperature belowTg0will increase depending on the thermal history the specimen was subjected to. In a preferred embodiment ofthe present invention, the heating time, the annealing time, the treatment configurations' sequence and the cooling method are realized based on how the structural change will affect the annealing time constant and the ductility of the ribbon. The thermal treatment is performed for the minimum time required to adequately relieve the residual and the series of applied stresses, which is dependent on the time constant associated with a chosen treatment temperature and with the evolution ofthe structural state during treatment. Going beyond this minimum time is unnecessary and will allowtoo much structural relaxation to occur which will be detrimental to the ductility of the ribbon. 20 The shorter time constant available for alleviating applied stresses occurs at the beginning ofthe treatment once the treatment temperature is reached. Accordingly, the residual and applied bending stresses are mainly relieved when reaching point 5 in Figure 1. Preferably, the travelling distance 

### d is kept short by placing roller2 very close to roller 1 to limitfurther structural relaxation. Preferably, the choice of roller 2 radius r2 is determined in order to obtain a cooled alloy ribbon showing maximum alleviated stresswhen bentatacurved radius closeto r1 aftertreatment. Preferably, the in-line annealed amorphous alloy ribbon is still in its amorphous state once the thermal treatment ends. However, in another embodiment, the thermal 30 treatment temperature and time may be increased in order to reach onsetWO 2011/060546 43 PCT/CA2010/001844

crystallization ofthe alloy. The choice oftreatmenttemperature and time can be set to end the thermal treatmentwith the alloy being partially or completely crystallized. Such use of the in-line annealing apparatus of the present invention can be advantageousforamorphous alloys requiring crystallization annealing. Referring now to Figure 2, the apparatus further preferably comprises a feeding ribbon reel 9 and a take-up mandrel 10. The ribbon reel mandrel and the other mandrel are respectively coupled via a shaft to a motor. In operation, one of the motors rotates to adjustthe ribbon speed while the other is in torque control modeto 10 regulate the mechanical tensile stress in the forwarding ribbon. Rollers 1 and 2 are free to rotate and are driven by the ribbon acting as a driving belt and the tensile stresses S1 and S2 arethe same.
In the apparatus of Figure 1, the treatmenttime on roller 1 at agiven ribbon feeding rate is proportional to contact angle 81 and the cooling time on roller2 is proportional to contact angle 82. Referring nowto Figures 3a and 3b, there are shown modified versions ofthe apparatus shown in Figure 1 which provides awidercontact angle 81 or 82 by adding a small guide roller 10 rotating in parallel and in close proximity to hot roller 1 or2. The guide roller 10 can either be located just afterthe entry point 3 20 orjust before the exit point 7 ofthe ribbon in its travelling path. In both apparatus, the ribbon feeding and take-up mandrels can be located at a remote location. The guide roller radius is preferably small to maximize 81 or 82. With the modified apparatus of Figures 3a and 3b, the ribbon feeding rate can be increased while keeping the same treatment time and temperature on hot roller 1 as for the apparatus shown in Figure 1. In Figure 3b, 82is also increased.
Since the stress relief action occurs mainly when the ribbon is near the treatment temperature, no significant stress relief is occurring while the ribbon is heating up starting from Tinoto reach the treatmenttemperature as shown in Figure 7a. The fullWO 2011/060546 44 PCT/CA2010/001844

angular distance (81 x r1) can be employed for alleviating stresses if the ribbon temperature Tin0 is nearthe treatment temperature when making contact at point 4 and preferably, in a state where structural relaxation has not made significant progress compared to its initial structural condition characterizing its as-cast state. This way, the treatment time on roller 1 at a given ribbon feeding rate and roller temperature can furtherbe increased.
In another preferred embodiment, the heating of the ribbon is performed before subjecting the ribbon to a series of treatment configurations. It is true that the 10 structural relaxation will commence, but the heating time in the present invention is comparable to the treatment time and, considering that the structural relaxation progression speed increases exponentially with the reciprocal of temperature and thatthe temperature is in a rising mode while being heated, no significant structural relaxation will occur if the rising temperature gets near the treatment temperature just a moment before the ribbon makes contact with hot roller 1. Referring now to Figure 4a, there is shown a modified version ofthe apparatus of Figure 1, where a second hot roller 11 having a radius r3 and rotating in parallel and in close proximity to roller 1 has been added. The travelling path of the ribbon has been modified to add the hot roller 11 in its path. Before making contact with roller 1 at point 4, the 20 ribbon makes a static contact with the hot surface of roller 11 at point 12, where it also bends to the hot roller radius r3 and starts to heat up at a high temperature rising rate. The ribbon is kept in contactwith the hot rollersurface foragiven rotation angle 83. While moving along with the hot roller 11 surface in rotation, the ribbon temperature goes up to a temperature below or equal to the hot roller 11 temperature. At point 13, the hot ribbon breaks contact with hot roller 11 and goes through in flat configuration to point4 ofthe hot roller 1 and follows the same route path as described for Figure 1. The resulting temperature profile is shown in Figure 7b. Preferably, while rotating along in contact with roller 11, the ribbon temperature is constantly in a rising mode. More preferably, when breaking contactwith roller 11WO 2011/060546 45 PCT/CA2010/001844

at point 13, the ribbon temperature has substantially reached the treatment temperature. The hot roller 1 heat sourcing or sinking is then adjusted to keep the incoming ribbon atthe treatment temperature while in contact for the whole rotating angle 81. Also, the hot roller 11 is placed in close proximityto roller 1 to minimizethe travelled path length between points 13 and 4 in the flat configuration between roller 11 and roller 1. The choice of roller 11 surface temperature, outer radius r3 and contact angle 83 is optimized to reduce temperature rising time in order to limit the progression of the structural relaxation before reaching point 4. A reduced temperature rising time is possible by setting the temperature of roller 11 above the 10 treatment temperature with the ribbon leaving roller 11 when its temperature gets nearthe treatmenttemperature in orderto benefitfrom the highertemperature rising rate ofthe initial portion ofthe negative exponential decay (_e-X ) closely followed by the ribbon temperature. Furthermore, any slow progressive change in the ribbon thickness, which would affect the temperature rising rate on roller 11 and therefore the ribbon temperature at the leaving point, can be compensated by correcting the temperature of roller 11. Such thickness changes can be easily detected by monitoring the power supplied to roller 1 for maintaining the treatment temperature on the incoming pre-heated ribbon. Anotherwayto further reduce temperature rising time is to use more than one hot roller 11 having a smaller outer radius and being 20 disposed side by side and in parallel for pre-heating the ribbon which follows a snaking path from one roller to the other. A ribbon snaking around multiple smaller hot rollers will heat up alternatelyfrom each side ofthe ribbon and more rapidly at a given tensile stress as the pressuring contact on a roller increases in an inversely proportional mannerwith respect to its outer radius. Alternately heating from each side of the ribbon also reduces the gradient temperature through the thickness as compared with heating from only one side, thus offering a more uniform temperature increasing rate through the ribbon thickness. At equivalent ribbon temperature rising rates, smaller rollers can therefore be used to reduce the ribbon tensile stress, thus lowering the risk of a breakage during treatment. In Figure 4b, the hot roller 11 ofWO 2011/060546 

### 46 PCT/CA2010/001844

Figure 4a has been replaced by two smaller rollers 11a and 11b of radius r3a and r3b. With this modified apparatus, the sum ofthe angular distances of both rollers 11a and 11b, 

### (83a Xr3a + 

### 83 bx r3b) can be made smallerthan the angulardistance 

### (83 x r3) of Figure4aforequivalent ribbon tensile stresses asthe ribbon temperature rises more rapidly as shown in Figure 7b, thus further limiting the progression ofthe structural relaxation before reaching point4.
In the present invention, the operation of heating and cooling the amorphous alloy ribbon by a direct static contact between one ofthe two side surfaces ofthe ribbon, 10 or alternately on each side, and along a significant peripheral portion of athermally conductive roller hasto take into accountthe thermal expansion orcontraction ofthe alloy. When submitted to atemperature change, the alloyseeks to expand while its temperature is rising, orto contractwhile itstemperature isfalling. This phenomenon will create concentrated surface shearing stresses atthe anchoring contact points of the ribbon with the surface ofthe rollerwhich are preventing the ribbon from slipping. During the heating stage of the in-line annealing process, as the ribbon seeks to expand with the temperature getting higher, the alloy viscosity drops and the appearing surface shearing stresses are getting relieved with increasing flow. Therefore, no significant surface shearing stresses will build-up while the ribbon is 20 heating up. However, this is a differentstory atthe cooling stages using cold rollers. As the temperature is falling, the ribbon seeks to contract while its viscosity increases rapidly. This will introduce increasing concentrated surface shearing stresses which can cause collapsing ofthe anchoring contact points and therefore an abrasive wearofthe surface ofthe cold rollerwill occur. In the present invention, this abrasive wear problem can be significantly attenuated by snaking the ribbon through multiple cold rollers over a series of small angular distances (8 x r) during the decrease in the ribbon temperature as shown in Figure 5. Jumping over multiple cold rollers will null the accumulating concentrated shearing stresses at each jump before they getto a point on the rollerwhere the abrasive wear becomes a seriousWO 2011/060546 47 PCT/CA2010/001844

problem. Ifcold rollers are used in the second cooling stage, their numberand each angular distance (8 x r) may be chosen according to a maximum admissible temperature drop LlTo on each roller as shown on Figure 7c and on the final temperature TFO atwhich the ribbon will betaken-up on a mandrel. Asforcold roller 2 in Figure 1 to 5, it is preferable to minimize the angular distance (82x r2) until the ribbon temperature ToutO, when leaving the roller at point 8, has dropped sufficiently belowthe treatmenttemperature to allowfurther ribbon handling while continuing to cool down without provoking further significant detrimental stress relief, otherwise avoidable abrasive wear will occur if dropping further below that point. Also, 10 repetitively nulling the accumulating concentrated surface shearing stresses will attenuate introduction of residual stresses which contribute in deteriorating the magneticproperties ofthe ribbon aftertreatment. Referring now to Figure 6a, there is shown a modified version of the apparatus shown in Figure 1 which is used for in-line annealing an amorphous alloy ribbon that will show maximum stress relief after treatment at a programmable radius r a. The controlling oftheflowsequence occurring in the alloyatthetreatmenttemperature is modified byfurther bending the ribbon on an additional roller rotating in contactwith the forwarded ribbon along the thermal treatment path. The apparatus further 20 comprises a roller 14 having a predetermined radius r4 and contacting the ribbon somewhere between point 5 and point 6 and parallel to rollers 1 and 2. While going from roller 1 to roller 2, the ribbon bends backwards on roller 14 on a contact angle 8

4 to relieve bending stresses opposite to the treatment bending side on roller 1. Depending on ribbon thickness and feeding rate, the choice of rollers' radius r1, r2 and r4, the temperature of rollers 1, 2 and 14 and the covering angle 81, 82, 8 4 are determined in order to obtain a cooled alloy ribbon showing maximum alleviated stress when bentto a radius ra greaterthan r2 aftertreatment. The radius ra can be programmed by either displacing roller 14 perpendicularly against the ribbon or by displacing roller 2 around roller 14 to increase or decrease the contact angle 84.WO 2011/060546 

### 48 PCT/CA2010/001844

Thisway, an amorphous ribbon could be in-line annealed to a radius ra progressively increasing as material is forwarded and contacting angle 84 is increased in orderto match the increasing bending radius when it is rolled toform a circularcore. Referring now to Figure 6b, there is shown an apparatus of the present invention which is used for in-line annealing an amorphous alloy ribbon in aflat configuration. This apparatus is similarto the apparatus shown in Figure 6a, but configured to inline anneal the ribbon at an infinite radius ra. Roller 1 serves mainly to heat up the ribbon in a similar manner as explained for roller 11 in Figure 4a. When the ribbon 10 breaks contact with hot roller 1 at point 5 and at the treatment temperature, it progresses forward at high speed in aflat configuration fora predetermined distance before making contact at point 15with roller 14. In this case, the desired stress relief is occurring while travelling at the treatment temperature in a flat configuration towards roller 14. The flat configuration treatment time becomes a function of the ribbon travelling distancefrom point 5to point 15 at a given ribbon feeding rate. The required flat configuration treatment time is very short in respect to the temperature decay time constant while travelling from point 5 to 15, so that no significant temperature dropwill have occurred when point 15will be reached. Although the flat treatment zone of the ribbon could be located within a furnace to maintain 20 temperature, this is not necessary in the present invention. When the hot ribbon touches roller 14, added bending stresses are relieved. The added relieved bending stresses will then be reverted when itwill be bent backwards at initial cool down on cold roller 2. Preferably, roller 14 and roller 2 are in close proximity. Depending on ribbon thickness and feeding rate, the choice of radius r2 and r4, the temperature of roller2 and 14, the covering angle82and 84and thetravelling distance between point 13 and 15 are determined in orderto obtain acooled alloy ribbon showing maximum alleviated stress in aflat configuration.WO 2011/060546 

### 49 PCT/CA2010/001844

The apparatus ofthe present invention shown in Figures 1 to 6 are best suited to inline anneal in a normal atmosphere an amorphous alloy ribbon such as iron-based Metglas 2605SA1 and 2605HB1 underan applied tensile stress with post-annealing limited orno acquired embrittlement. Magneticproperties ofamorphous alloy ribbons 2605SA1 and 2605HB1 have been greatly improved after theywere in-line annealed at high speed with the apparatus ofthe present invention. Magnetic performances of rolling-up-after-annealing circular cores compare favourably to circular cores processed using the conventional field furnace anneal,ing method.
10 Referring now to Figures 9 to 13, there is shown a detailed construction of a hot roller. The hot roller comprises an inner heat source ring 16 and an outer cladding heat diffuser ring 17 rotating together around a central axis 13. The outer cladding ring 17 is made of a good thermal conductive material, such as copper, and has a predetermined thickness e2. If the chosen material is prone to severe oxidation at high temperatures which eventually leads to mechanical degradation, as it is the case for copper, its exposed surface may be plated with athin metal film 17a having a substantial stainless property, such as nickel, to protect its surface from severe oxidation. The inner ring 16 is made of an electrically resistive conductor material. The electrical resistive conducting nature ofthe inner ring 16 serves as a means to 20 produce heat by ajoule effect of circulating currents. Ring 16 could be omitted if a burning flame would be used to heatthe thermal diffuserfrom underneath. With ring 16, such produced heat may be generated by an electrical self heating element ring 16 provided with two electrical conductors that are connected outside ofthe ring to a current source via a pair of sliding contacts located somewhere along the ring rotating axis 13. Preferably, the inner ring 16 is made of an electrically resistive conductor material such as stainless steel, and has a predetermined thickness e1. To provide an efficient heattransferand from the inner ring 16 to the outer cladding ring 17, preferably, the outer cladding ring 17 is welded or is build up on ring 16 by using an electroplating process after which the outer surface of the ring 17 is 30 machined. Heat can also be produced by electrical induced internal AC currentsWO 2011/060546 

### 50 PCT/CA2010/001844

which are looping in the ring. The current loops are induced by a high frequency fluctuating magnetic field produced with an induction heating antenna 18 and are looping following the circular path delimited by the ring 16. The induction heating antenna 18 is essentially made of insulated copper tubing which is cylindrically coiled, aligned, centered and fixed within the hollow portion of ring 16 and which is also separated from it by an air gap 18a. Coolant is allowed to flow within the antenna copper tubing to evacuate the coil conducting joule losses. Preferably, the thickness e1 of ring 16 is greaterthan the skin depth ofthe induced AC currents at the antenna powersupplyfrequency. The copper cladding thickness e2 is chosen to 10 be thick enough so to act as a thermal diffuser to ensure uniform heat distribution and transfer from the heated inner ring 16 to the ribbon in contact with the outer cladding ring 17. The two-ring assembly 19 has a much greater thickness when compared to the ribbon thickness and serves, with its thermal inertia, as a heat buffer reservoir to level the temperature all around the periphery when heating a ribbon that is moving along in contactwith the rollersurface in rotation. The two-ring assembly 19 is at least as wide as the ribbon width

. To support the two-ring assembly in rotation, extending thin tube walls 20 having a thickness e3 protrude from both sides ofthe inner ring 16. Thetubewalls 20 are preferably made ofa poor thermal conducting material such as stainless steel and the wall thickness e3 is 20 made sufficiently thin to limit heat leakage towards the tube walls opposite extremities but, is made sufficientlythickto supportthe pulling forces exerted bythe ribbon in tension on the roller surface in order to maintain concentricity while the roller is rotating. The tube walls opposite extremities each have a thickerwall 21 for receiving holding flanges 22. If the tube walls 20 material are made of stainless steel, as it is preferably the case, induced current loops will extend beyond both sides ofthe inner ring 16. This side effectwill generate parasitic heatwithin the tube walls. Therefore, the tube walls 20 are provided with axial periodically spaced slots 23, slotted from the edges of both sides of the stainless steel ring 16 on a length long enough to breakthe circular path loopfor induced currentto flowthrough within 30 the vicinity of the two-ring assembly 19. Moreover, these slots create finger-likeWO 2011/060546 51 PCT/CA2010/001844

supporting means for holding both sides of the two-ring assembly and which can bend radiallyto accommodate thermal radial expansion ofthe two ring assembly 19 while keeping it concentric with the rotating axis. As shown in Figures 12 and 13, each side flange 22 comprises a hollow shaft 24 supported on bearing 25 which is inserted in an opening of wall 27. In an inverted version, the opening 26 may be localised in flange 22 with shaft 24 being incrusted in wall 27. To allow the axial thermal expansion ofthe two-ring assembly 19 and ofthe tube walls 20, aspring 28 is inserted on the shaft 24 between flange 22 and bearing 25, and the shaft and bearing are allowed to slide one onto the other. The induction heating antenna 18 is 10 supported in its central hollow portion bythe supporting means 29 which is attached to the shaft 30 that passes freelythrough the hollow portion ofthe shaft 24 in order to be held from outside of the roller by the plate 31 which is secured on the supporting structure wall 27. The two insulated coppertubing ends 18a and 18b of the induction heating antenna 18 extend freelythrough the opposite hollow shaft 24 to reach the HF electrical AC power supply. Therefore, the hot roller is allowed to rotate on both supporting bearings while the induction heating antenna 18 remains fixed withoutphysical interferencewith the hot roller. Referring nowto Figure 14, there is shown a cutview ofa detailed construction ofa 20 cold roller. The cold rollercomprises athermal conducting ring 32 having athickness e4 and being supported by side flanges 33. The junctions between the thermal conducting ring 32 and the flanges 33 are provided with a seal 34. The cold roller also comprises an inner part 35 having an outer cylindrical surface 36 centered within the hollow portion of the thermal conducting ring 32 and from which it is separated by a small gap. The inner part 35 is held bythe two side flanges 33 with attaching means. The side flanges 33 are each provided with a central recess to insert and hold the outer rotating part of a bearing 37. The side flanges 33 also comprise atube tip 38 protruding from the center ofthe flange to allow a coolant to passthrough. At least one opened path link 39 is provided within both extremities of 30 the inner part 35 to allow the coolant flowing in the tube tip to reach the gap.WO 2011/060546 52 PCT/CA2010/001844

Therefore, coolant entering in one ofthe two tube tips 38 will be guided through the gap in contact with the inner surface ofthe thermal conducting ring 32 to exchange heat. Then, the coolant follows its way out via the other tube tip at the opposite flange location. The cold rollerassembly is supported bythe inner rotating partofthe bearings 37 on two hollowshafts 40 fixed to awall structure. The tube tip 38 rotates in the hollow portion ofthe shaft 40 separated from the shaft innerwall by a sliding seal 41. Preferably, the coolant fluid is water. A higher ribbon cooling rate can be obtained using asub-zerotemperaturefluid such as glycol.
10 In the cold rollerof Figure 14, the ribbon falling temperature is quickeron one side of its edge as the coolant is getting hotter while flowing underneath the thermal conducting ring 32 from one sidetothe other. Referring nowto Figures 15aand 15b, there is shown a modified version ofthe cold rollerthat distributes incoming coolant uniformly underneath the thermal conducting ring 32. The central portion 36 has been replaced by a stackofthin discseparators 42 spaced apart byspacers 43 and 43a. The discseparators 42 diameter is slightly smallerthan the thermal conducting ring 32 inner diameter in order to create a small gap 44. The spacers 43 and 43a have a smallerdiameterthan the discs 42 to create a gap 45 for distributing to and collecting coolant from gap 44. Two series of parallel aligned openings 46 and 47 20 are perforated through the center portion ofthe stacked arrangement with each of the spacers having atransverse opening 48 between the corresponding gap 45 and one of the two parallel openings in an alternate stacked order. The parallel and transverse openings 46, 47 and 48 then form two manifolds, one intake and one outtake. Two spacers 43a are respectively located at both ends of the stacked arrangement to connect each tube tip 38 to a corresponding manifold which will allow coolant flowing in one tube tip 38 to be distributed via the outtake manifold in one outofthe two gaps 45 and to reach the innerwall ofthe thermal conducting ring 32. The coolant will then return to the intake manifold via the small gap 44 and the corresponding gaps 45 and will exitthe rollerviathe tube tip atthe otherextremityof 30 the roller.WO 2011/060546 53 PCT/CA2010/001844

When processing a ril;>bon unrolled from a reel, the ribbon may travel with some sideways instability due to some factors like the sourcing reel being warped. Ifthe ribbon necessarily has to pass by a precise location on a roller, as required on a hot rollerofthe present invention, amechanism must be used tofixthe ribbon trajectory. Preferably, the present invention further comprises a device to deliver a ribbon at a precise location on aguiding roller. Referring to Figure 16, there is shown a pivoting roller 115 rotating on an axis 118 10 and provided with two guiding side flanges 116that are each inclined and which are separated by a distance just slightly greater than the ribbon width. The roller 115 also has aswivel axis 117tangential to its peripheral surface and located at midpoint between the flanges 116. The ribbon is guided onto the roller surface over a given angle 

## a up to the tangential point with the swivel axis where it exits. The travel trajectory is best corrected if the ribbon entry point on the roller is at 180 degrees with respect to the exit point. From an observerview point looking atthe rollerfrom the left as shown in Figure 16, a ribbon entering the roller with some sideways instability (for example: ribbon axis fluctuating back and forth from position in1, in2, in3) will swivel the roller by pushing on the roller flanges with its edges so that the 20 entry point will continuously be aligned with the incoming ribbon axis, and the outgoing ribbon will always exit the roller on the same axis (out1, out2 and out3 aligned together). The radius ofthe swivel guiding roller is chosen in relation to the ribbon width and to the magnitude ofthe lateral instability. A bigger roller diameter will swivel less to correctthe same sideways instability. When the roller swivels, the incoming and outgoing portions of the ribbon will slightly twist on their axis. Therefore, the swivel roller must be located at some distance from other guiding rollers in order to allow some free space for the ribbon to slightly twist as it approaches orexitsthe rolleras shown on Figure 17.WO 2011/060546
54 PCT/CA2010/001844

When processing a ribbon at a high feeding rate with an added tensile stress, trying to control said tensile stress by controlling the torque on the unrolling source reel and the torque on the rolling up take-up mandrel as shown in Figure 2 is less convenient because of the following reasons: large quantity of rolled up material have a high inertia; a ribbon loosely rolled up on a mandrel may suddenly slip when unrolled with a tensile stress; and it may be desired to roll up the ribbon at a lower tensile stress than required for treatment to limit the tightening radial force accumulating in the rolled up ribbon. Preferably, the present invention comprises an 10 apparatus to drag a ribbon and to change the mechanical tensile stress in a forwarding ribbon at a passage point in its traveled path. The drag and tensioning system usesthe staticfriction between two surfaces in contactwith each other.
The ratio of the maximum applicable force F 

### s that can be applied on an object leaning on a surface without slipping to the normal force F nexerted bythe object on the surface is the coefficient of static friction J.ls. As long as the applied force is inferiorto Fs, the objectwill not move.



### 20 The staticfrictional force also acts on a ribbon surrounding the outer perimeter of a wheel overan angle

### 0 with atensile force. Figure 18a illustratesthis situation. In this case, we are assuming thatthe wheel cannot rotate. Two tensile forces, Fin and Fout, of different values are exerted on the ribbon on either side of the wheel. By these forces, the ribbon strangles the wheel and also exerts a normal force to the surface ofthe wheel that puts in action the mechanism ofstaticfriction. As forthe objecton a surface, the difference ofthe two forces is opposed by a staticfriction force ofsame amplitude between the wheel and the ribbon surfaces that prevents the ribbon from slipping. When the difference in applied forces reaches the staticfrictional limitforce,WO 2011/060546 55 PCT/CA2010/001844

the ribbon starts to slip on the wheel. The maximum exerted forces between the inputand the outputcloselyfollows this equation: 

# F
- F ef-LS¢ out
- in
Therefore, for two tensile forces exerted on the ribbon on either side of the wheel overan angle 

### 0, the ribbon will startto slip when the outputforce will be superiorto Foutfor agiven inputforce Fin and static coefficient offriction Jls. The tensile force in the ribbon along the surface ofthewheel will have an exponential profile as shown in 10 Figure 18b. This is known asthe capstan effect.
Staticfrictional capstan drives are used in the present invention to drag the ribbon at a high travelling speed either to control its speed or to increase or reduce the mechanical applied tensile stress. The dragging apparatus allows: 1. Smoothertensile stresstransition. 2. Uniform distribution ofthe applied tensile stress along thewidth ofthe ribbon. 3. Precise control on the added tensile stress amplitude. 4. Precise control ofthe ribbon feeding rate. 5. The amplitude of the desired added tensile stress can be independent from 20 the staticfriction coefficient.
1. SmootherTensile StressTransition Any attempts to increase the tensile stress in a forwarding and tense thin alloy ribbon within a short distance on a point along a travelled path will create a continuous step up stress transition level on the ribbon material. If the ribbon is forwarded at great speed, the transition time will be very short and, if the added tensile stress is high, the ribbon will be submitted to a strong mechanical shock and therefore risks breakage. In the present case, a tensile force is gradually addedWO 2011/060546 

### 56 PCT/CA2010/001844

along the covering angle ofthe capstan wheel in contactwith the ribbon. Therefore, the stress step-up transition time can be considerably increased by using either a large diametercapstan wheel orby using multiple cascaded smallercapstan wheels, thus ensuring acontinuous high speed reliablefeeding ofatight ribbon.
2. Uniform Distribution of the Applied Tensile Stress along the Width of the Ribbon
For large ribbons, uniformly distributing the increasing tensile stress along the width 10 of the very thin ribbon is necessary. For high tensile stresses, a non-uniform distribution of the stress combined to any potential physical defects, like a small inclusion at the ribbon edge, can tear the ribbon apart from the edge. With the capstan drive, the ribbon lies on a uniform surface and the tensile stress is progressively added over a significant length, thus avoiding any significant imbalance oftensileforces along thewidth ofthe ribbon.
3. Precise Control on theAdded Tensile StressAmplitude
The added tensile stress on the ribbon is performed by applying a clockwise or 20 counterclockwise torque on the capstan wheel. High precision torque can be easily provided by atorque regulated electrical motor mechanically coupled to the capstan wheel axis of rotation.
4. Precise Control ofthe Ribbon Feeding rate By using a capstan wheel in static friction mode with the ribbon, the wheel surface tangential speed is synchronised with the ribbon feeding rate. It is therefore easyto precisely control the ribbon feeding rate by controlling the capstan wheel rotating speed. In asystem where a ribbon is unrolled from a reel to anotherwhilefollowing a 30 path through a series of rollers and capstan static friction drives, it is possible toWO 2011/060546 

### 57 PCT/CA2010/001844

control the feeding rate ofthe ribbon ifrotation ofone ofthe capstan drives is speedcontrolled and that all other drives are torque-controlled. The speed control of the capstan wheel can easily be performed using a speed controlled motor drive mechanicallycoupled tothewheel axis ofrotation.
5. The Amplitude ofthe Desired Added Tensile Force can be Independentfrom the Static Friction Coefficient Regardless of the coefficient of static friction, any amount of tensile stress can be 10 added or subtracted from a point along the path of the forwarded ribbon. The maximum tensile stress that can be applied fora given coefficient ofstaticfriction is limited bythe number of capstan wheels encountered bythe ribbon on its travelling path. Figures 19a/19b and 20a/20b show examples of a staticfriction capstan drive used for adding or subtracting a tensile stress on a forwarded amorphous alloy ribbon having a given tensile stress. The capstan wheel is made ofaluminum and its outer periphery is covered with rubber to increase the coefficient of static friction. Two rollers are placed side byside nearthe outerperipheryofthe capstan wheel to guide 20 the ribbon in and outofthewheel surface. Referring to Figure 21, there is shown a static capstan ribbon drive apparatus to impose a mechanical tensile stress Sc between an incoming ribbon having an input tensile stress SIN and the outgoing ribbon having an output tensile stress SOUTo The apparatus comprises two capstan static friction driving wheels 110 each provided with a pair of guiding rollers 112. Preferably, the outer surface periphery of each capstan wheel is covered with a high friction coefficient material such as silicon rubber. The incoming ribbon is guided by the guiding rollers 112 to wrap around each capstan wheel 110 overthe maximum covering angle possible. Each capstan 30 wheel is mounted on a shaft of a motor. To control Sc, the shaft torque Trq1 isWO 2011/060546
58 PCT/CA2010/001844

adjusted to produce atangential force atthe radius r ofthe wheel that will be added on the incoming ribbon having an inputtensile stress SIN in order to get the desired tensile stress Sc once the ribbon exits from the capstan wheel. The tensile stress is changed again to an output value SOUT by passing over the second capstan wheel, in which the shaft torque is adjusted to Trq2. For example, to increase the tensile stress on a ribbon between the two capstan wheels, a positive counterclockwise Trq1 and a clockwise torque Trq2 is required. For ribbons travelling at high speeds, multiple capstan wheels are used as shown in Figure 22. The ribbon travels in a snake path around the wheels, each driven by afraction Trq1 (a-d) ofthe total torque 10 Trq1 in order to add the tensile stress in a series of smaller steps. Use of multiple capstan wheels for decreasing the tensile stress is not necessary as the ribbon can easilywithstand a sudden step down in tensile stress. Referring back to Figure 1 to 6, any ofthe rollers included in the in-line annealing apparatus can be provided with a shaft coupled directly or via a drive-belt to a motor to add or subtract a tensile stress on the guided ribbon. It has been found that the reduced viscosity at elevated temperature of an amorphous alloy ribbon significantly increases the friction coefficient with the roller surface it is in contact with. Therefore, the tensile stress within the ribbon can be changed along the treatment path by applying a torque on rollers 1, 2 11 or 14 to improve annealing and the magnetic the properties of the 20 alloy. Figure 23 discloses an apparatus to continuously in-line anneal aferromagnetic alloy ribbon unrolled from a reel 136 which will then be rolled up on a mandrel 135. The apparatus comprises: two tensioner rollers 130; an apparatus to laterally reposition an incoming ribbon 131; a first drag and tensioning system for a moving thin ribbon 132; an apparatus to in-line anneal a forwarding ribbon 133; a second drag and tensioning system for a moving thin ribbon 134; and a take up mandrel 135. A tensioner roller 130 is commonly used in the art for providing easier control on the tension of a ribbon unrolling from or rolling up on a large roll of ribbon. Preferably,WO 2011/060546
59 PCT/CA2010/001844

the feeding rate of the ribbon within the apparatus is controlled by controlling the capstan wheel rotating speed in the drag and tensioning system 134. Preferably, the in-line annealing process of Figure 23 includes an automated ribbon switcher to provide uninterrupted forwarding of ribbon at the entry of the treatment process, and continuous rolling up onto take-up mandrels ofoutgoing treated ribbon. Continuous forwarding of ribbon can be provided by bringing a new reel of ribbon in rotation in proximity of the emptying reel, and by launching and welding the ribbon end of the new reel to the trailing end of the ribbon leaving the emptying reel. 10 Continuous rolling up of outgoing treated ribbon can be provided by bringing a new mandrel in rotation in proximity ofthe filling mandrel, and by cutting the ribbon and fixing the incoming ribbon end to the new mandrel while the filled mandrel is moved away.
A prototype was built according to the above-described in-line annealing process of Figure 23 to process a one-inch wide amorphous alloy ribbon at a constant ribbon feeding rate. Referring nowto Figure 24, there is shown the detailed configuration of the in-line annealing setup 133. It comprises two identical hot rollers 1 and 11 built using wall thickness e1 and e2 of 100 mils and e3 of 25 mils. The heat source two20 ring assembly 19 is 1.10 inches wide and the roller outer radius is 3 % inches. The slotted walls 20 are afew inches long on both sides ofthe two-ring assembly 19 and are supported on flanges and bearings. Figure 11, 12 and 13 are scaled perspective and cut views of the hot roller built according to the present invention. Both hot rollers are located in order to be separated by a gap smaller than 1/32 inch when hot. Each hot roller comprises an induction antenna connected to a HF power supply operating respectively at a frequency of 80 kHz and 150 kHz to avoid magnetic coupling interferences between proximity antennas. The hot roller 11 acting as a ribbon heating roller could also be disabled just by shutting off its corresponding HF power supply if no pre-heating was desired, in which case it was 30 simply used as a guiding roller. The setup also comprises two cold rollers 2 and 51.WO 2011/060546 60 PCT/CA2010/001844

Cold roller 2 has a 5/8 inch radius and is used forfirst stage cooling. Cold roller 51 has a 3 inches radius and is used for the second stage cooling to bring the temperature towards or above the water temperature. The ribbon leaving roller 51 will be taken-up on a mandrel where it will slowly go back to normal room temperature. Both rollers were supplied with cooling water at 20 degrees Celsius. When snaking the ribbon around roller 1 and 2, the contact angle 81 on the hot roller 1 is near 210 degrees and 82 on cold roller 2 is near 120 degrees. A first infrared pyrometer 49 was installed to measure the ribbon temperature just after leaving roller 1. A second infrared pyrometer 50 was also installed to measure the 10 temperature on the outer surface ofthe pre-heating roller 11. The pyrometers were connected to acomputer used as acontrollerto adjustthe antennas respective input powerin orderto read the desired temperature ateach pyrometer. When pre-heating on roller 11 was activated, the roller temperature and the contact angle 83 were adjusted by relocating a guide roller 10 around roller 11 until the rising temperature reached the treatmenttemperature afew angulardegrees before reaching exit point 13. The treatment temperature was then maintained on hot roller 1. The treatment setup of Figure 24 is intended to in-line anneal an iron-based amorphous ribbon in a curved shape having a natural bending radius in a rest position close to 3

### Yt inches aftertreatment. Such a bending radius is close to the average bending radius found 20 in a circular core of a 25 kVA distribution transformer as disclosed in US patent 5566443. The ribbon was unrolled at a tensile stress of a few MPa from a source reel and forwarded at different feeding rates snaking around four capstan wheel drives to increase the ribbon tensile stress to S1 before going through the treatment and then, afterleaving treatment atthe sametensile stress S2 

### = S1, itwent overone capstan wheel drive to reduce the ribbon tensile stress to a few MPa before being taken-up on a mandrel. All source reel mandrel, rolling mandrel and capstan wheels were coupled to motors controlled by a drive system and a main computer. The whole setup including motors and drives, except for the HF power supplies and computer, was mounted on a 4' x 8' table, thus illustrating the compactness oftheWO 2011/060546

61 PCT/CA2010/001844

apparatus of the present invention. Figures 7a and 7b give the two temperature approximate profiles that the ribbon was subjected to while moving along its travelling path within the setup. In Figure 7a, no pre-heating on roller 11 is performed. The ribbon is heated and treated only on hot roller 1. Fora given ribbon tensile stress, the heating rising time interval is independent of the ribbon feeding rate. Therefore, for high feeding rates, the heating temperature rising time will start to dominate as the time period the ribbon rotates along the surface of hot roller 1 gets shorter (due to the increasing feeding rate) and therefore leaving less time for the treatment time interval on roller 1 to act. The ribbon will have an upperfeeding 10 rate limit where the treatment efficiency on roller 1 dramatically deteriorates. In Figure 7b, the added pre-heating roller 11 eliminates the heating time interval from the time period the ribbon rotates along the surface of hot roller 1 which nowserves exclusively for treatment. This setup will push-up the ribbon feeding rate limit for a treatmenttime on roller 1 identical to the situation in Figure 7a ifthe initial cool down on roller2 is sufficientto end thethermal treatment.
Series oftreatments at applied differenttensile stresses (S1 =S2) ranging from 25 to 200 MPa and at different treatment temperatures above 

### 400D

### C and feeding rates ranging from 1 to 5 m/sec were conducted with the apparatus on the amorphous 20 alloy ribbon Metglas 2605SA1 and 2605HB1 supplied by Hitachi-Metals. At 1 m/sec, the thermal treatment was lasting less than a second in the built apparatus. At 5 m/sec, the thermal treatment was lasting less than one tenth of a second. During treatment, it is desired to subject the ribbon to the smallest tensile stress which provides acceptable magnetic properties improvements, as further increasing the tensile stress will only increase the risk of rupturing the ribbon. The heating temperature rising rate starting at tensile stresses of 25 MPa and at the hot roller mentioned diameterwas found to be greaterthan 103 DC/sec, above 104 DC/sec at about 75 to 125 MPa, therefore showing the high heat transfer capacity of the pressure static contact ofthe thin ribbon on the hot roller. Forthe first cooling stage, 30 thetemperature falling rate was found to be greaterthan 104 DC/sec and close to 105WO 2011/060546 62 PCT/CA2010/001844

°C/sec on cold roller 2. Following the treatment, the natural bending radius in a rest position was measured. Then, approximately 1 kg ofthe treated material was rolled at a chosen tensile stress on a stainless steel hub having an outer radius of 2.9 inches. With the amount of rolled up material, the final circular core had a mean radius atabout 3 }4 inches, which is close tothe radius of roller 1 in the apparatus of Figure 24. The rolled up ribbon was then placed in a circular shell and two copper wires were coiled around the shell toform adrive and asense coil. The shell served as a support frame for the coils to avoid any outside stress to be applied onto the core. The drive and sense coil were then connected to aWalker Scientific AMH-25 10 instrument which serves to characterize the magnetic properties of coiled ferromagnetic cores. Before performing a measurement, parameters related to the circularcore netcross sectional area and mean path length, the drive and sense coil respective turns and the material density, were entered in the instrument software. The sample was then magnetized with a sinusoidal magnetic induction waveform at a frequency of 60Hz. From the recorded hysteresis loop, the following parameters were computed: the material core loss; the exciting power; and the peak magnetic field, all at specific magnetic induction levels and, the Bso and Bso/Bsat ratio were noted. Significant effects of the thermal treatments on the amorphous alloys were**ob~erved** attreatmenttemperatures above425°C. 20 For the Metglas 2605SA1 material, good results were obtained at treatment temperatures above 425°C, more preferably above 450°C, more preferably at about 480°C, and increasing with ribbon feeding rate. Going beyond this temperature until onset crystallization was reached and at the corresponding feeding rate did not provide further significant improvements to the magnetic properties of the alloy. It rather unnecessarily prolonged structural relaxation, which was detrimental to the ductility of the ribbon. An efficient induced magnetic anisotropy was obtained at tensile stresses between 25 and 200 MPa, preferablybetween 75 and 125 MPa.WO 2011/060546 63 PCT/CA2010/001844

For the Metglas 2605HB1 material, an efficient induced magnetic anisotropy was obtained at tensile stresses between 25 and 200 MPa, preferably between 50 and 100 MPa. Low core loss was obtained at treatments temperatures above 400°C, more preferably above 425°C, more preferably at about 455°C. Going beyond this temperature until onset crystallization was reached and atthe corresponding feeding rate did not provide further significant improvements to the magnetic properties of the alloy. It rather unnecessarily prolonged structural relaxation, which was detrimental to the ductilityofthe ribbon. Also, core losswas tending to reduce as the ribbon feeding rate was increased along with thetreatmenttemperature, showing the 10 advantages ofa higherand short lasting treatmenttemperature.
When onset crystallization was reached for both alloys, the degree of crystallization was dependant on the adjusted treatment temperature above onset crystallization thus, making possible to usethetreatment process ofthe present invention to initiate and control the degree ofcrystallization in an amorphous alloy ribbon.
The following examples taken from the series of conducted treatments show the benefits ofthe present invention to improve magnetic properties ofamorphous alloy ribbon such as the 2605SA1 and 2605HB1. 20 Example 1:
Material: Metglas2605SA1 Ribbon feeding rate: 2.0 meters/sec Ribbon applied tensile stress: 100 MPa No pre-heating Treatmenttemperature: 480°C Natural bending radius aftertreatment: between 3.0"to 3.5" Ribbon rolled uptensile stress: 5 MPa 30 Coreweight: 1.04 kg (excluding hub)WO 2011/060546 64 Core innerdiameter: 5.80 inches (excluding hub) Core outerdiameter: 6.83 inches Core loss @ 1.3Tesla, 60Hz: 0.20W/kg Exciting power @ 1.3Tesla, 60Hz: 1.76VAlkg Peakmagneticfield @ 1.3Tesla, 60 Hz: 80Aim Bao: 1.3Tesla Bao/Bsat: 0.83 Example 2: 10 Material: Metglas 2605SA1 Ribbon feeding rate: 5.0 meters/sec Ribbon applied tensile stress: 100 MPa Pre-heating angle 

### 83: near 180 degrees Pre-heating rollertemperature: 485°C Treatmenttemperature: 485°C Natural bending radius aftertreatment: between 3.0" to 3.5" Ribbon rolled up tensile stress: 5 MPa Coreweight: 1.04 kg (excluding hub) 20 Core innerdiameter: 5.80 inches (excluding hub) Core outerdiameter: 6.83 inches Core loss 

### @ 1.3Tesla, 60Hz: 0.20W/kg Exciting power @ 1.3Tesla, 60Hz: 2.37VAlkg Peak magneticfield @ 1.3Tesla, 60 Hz: 97Aim Bao: 1.27Tesla Bao/Bsat: 0.81 Example 3:
30 Material: Metglas 2605HB1 PCT/CA2010/001844WO 2011/060546 65 Ribbon feeding rate: 2.0 meters/sec Ribbon treatment applied tensile stress: 75 MPa Treatmenttemperature: 455°C No pre-heating Natural bending radius aftertreatment: between 3.0" to 3.5" Ribbon rolled up tensile stress: 5 MPa Coreweight: 1.04 kg (excluding hub) Core innerdiameter: 5.80 inches (excluding hub) Core outerdiameter: 6.83 inches 10 Core loss @ 1.3Tesla, 60Hz: 0.14W/kg Exciting power@ 1.3Tesla, 60Hz: 0.19VAlkg Peakmagneticfield @ 1.3Tesla, 60 Hz: 6.6

### AIm Core loss @ 1.4Tesla, 60Hz: 0.18W/kg Exciting power @ 1.4Tesla, 60Hz: 0.35VAlkg Peak magneticfield @ 1.3Tesla, 60 Hz: 16.2

### AIm Core loss @ 1.5Tesla, 60Hz: 0.22W/kg Exciting power @ 1.5Tesla, 60Hz: 1.56VAlkg Peak magneticfield @ 1.3Tesla, 60 Hz: 80

### AIm Bao: 1.5Tesla 20 Bao/Bsatt: 0.91 Example4:
Material: Metglas 2605HB1 Ribbon feeding rate: 5.0 meters/sec Ribbon treatment applied tensile stress: 75 MPa Treatmenttemperature: 460°C Pre-heating angle 83: near 180 degrees Pre-heating rollertemperature: 460°C 30 Natural bending radius aftertreatment: between 3.0" to 3.5" PCT/CA2010/001844WO 2011/060546 66 Ribbon rolled uptensile stress: 5 MPa Coreweight: 1.04 kg Core innerdiameter: 5.80 inches (excluding hub) Core outerdiameter: 6.83 inches (excluding hub) Core loss 

### @ 1.3Tesla, 60Hz: 0.13W/kg Exciting power @ 1.3Tesla, 60Hz: 0.17VA/kg Peakmagneticfield 

### @ 1.3Tesla, 60 Hz: 6A/m Core loss @ 1.4Tesla, 60Hz: 0.18W/kg Exciting power 

### @ 1.4Tesla, 60Hz: 0.33VA/kg 10 Peakmagneticfield @ 1.4Tesla, 60 Hz: 15A/m Core loss 

### @ 1.5Tesla, 60Hz: 0.22W/kg Exciting power 

### @ 1.5Tesla, 60Hz: 1.55VA/kg Peakmagneticfield 

### @ 1.5Tesla, 60 Hz: 80A/m Bao: 1.5Tesla Bao/Bsat: 0.91 PCT/CA2010/001844

The core loss and exciting power measured on the above circularcores made with a rolled up ribbon in-line annealed at 5 m/sec are set forth in table 1 with those reported by the alloy manufacturer with field furnace annealing. Core loss for field 20 furnace annealed 60g SA1 and HB1 toroidal samples was reported in atable bythe alloy manufacturer in an article entitled "Advances in Amorphous and Nanocrystalline Magnetic Materials", by Ryusuke Hasegawa in Journal of Magnetism and Magentic Materials, 2006, vol. 304, 187-191, Table 2. Exciting powers for furnace annealed rectangular-wound-cut cores weighting 73 kg for SA1 and 75 kg for HB1 samples were deduced from plotted curves traced by the alloy manufacturerin an article entitled "Audible Noise From Amorphous Metal and Silicon Steel-Based Transformer Core", by Daichi Azuma and Ryusuke Hasegawa in IEEE Transactions on Magnetics, vol. 44, no. 11, 4104-4106, Figures 2 and 4. By comparison, rolling-up-after-annealing cores produced with the present invention 30 using Metglas 2605SA1 and 2605HB1 amorphous alloys are showing significantWO 2011/060546


### 67 PCT/CA2010/001844

lowercore loss, especiallyfor2605HB1. Exciting power is lower up to 1.4 Tesla but higher at 1.5 Tesla. The Bao/Bsa! ratio remains higher for furnace annealed cores compared to the present roll of in-line annealed ribbon due to introduction of some allowed stresses in the roll.
The examples disclosed above showthe efficiency ofthe method and apparatus of the present invention to in-line anneal an iron-based amorphous in a post-treatment state which is usable for making rolling-up-after-annealing cores having: reduced core loss compared to conventionally field furnace annealed cores; low exciting 10 power; a Bao greater than about 1.3 Tesla; and a Bao/Bsa! greater than 0.80. The 2605HB1 alloy has an even better Bao/Bsa! ratio which is greaterthan 0.90. As it can be observed, the optimal treatment temperature differs for the 2605SA1 and 2605HB1 at equivalent ribbon feeding rates. This difference is linked to the alloy composition. The optimal setting of the treatment temperature in the present invention istherefore dependanton the alloycomposition.WO 2011/060546 68 PCT/CA2010/001844

B= 1.3T B = 1.4T B = 1.5T

60Hz 60Hz 60Hz W/kg VA/kg W/kg VA/kg W/kg VA/kg 2605SA1 0.27 -0.4 Furnace annealed 2605SA1 0.20 2.37 present invention 2605HB1 0.24**~0.4** 0.29 0.5 0.38 1.0 Furnace annealed 2605HB1 0.13 0.17 0.18 0.33 0.22 1.55 presentinvention Table 1 Examples shown above were conducted on a test bench where the ribbon feeding rate was limited by some ofits mechanical and electrical elements ratherthan bythe geometric configuration of the hot and cold rollers. With the high cooling rate obtained in the present invention on cold roller 2, in-line annealing a ribbon at feeding rates up to 20 m/sec is expected with the above test bench by adding a second hot roller 11 and asecond cold roller51, if required. Also, an apparatusto in10 line anneal a ribbon for larger circular cores will require scaled-up rollers. As the annealing treatment is mainlyafunction oftemperature and time, ascaled-up design will allow a proportional ribbon feeding rate increase. Forexample: ifa similar setup as shown in Figure 24 was used for in-line annealing a ribbon in a curved shape having twice the final radius, than the ribbon feeding rate could go up as high as 40 m/sec. Therefore, the apparatus ofthe present invention can be efficiently used for massively in-line annealing an amorphous alloy ribbon in a curved shape. As the casting process for making an amorphous alloy is performed at a speed near 30WO 2011/060546 

### 69 PCT/CA2010/001844

m/sec, adding an in-line annealing unit at the output of the casting line could be foreseen.
In the present invention, the ribbon is continuously in-line annealed at a high feeding rate with an impulse heat treatment which limits the progression of structural relaxation and therefore has a different impact on the ribbon embrittlement compared to conventional field furnace annealing. For ribbons that are continuously in-line annealed with the apparatus ofthe present invention, once the ribbon exits the treatment, it must be handleable in orderto roll up the material on mandrels, and 10 it also needs to be cuttable in orderto allow easy switching ofthe rolling up ribbon from a filled mandrel to an new mandrel, or to continuously roll up ribbon to form cores in series. Any loss ofductility following the annealing treatment of iron-based amorphous alloy ribbons will increase the potential event of a ribbon break, which will lowerthe yield in the production ofannealed ribbon reels orcores, and cause an increase of cost. This yield will reduce further if the ribbon is moving under a significantamountofappliedtensile stress. Amorphous iron-based alloy ribbons, which normally become brittle when annealed in a furnace and that have been annealed with the apparatus of the present 20 invention, show good ductility characteristics. To best qualifythe degree of ductility ofthe ribbons annealed with the apparatus ofthe present invention, three methods are used. Ductility is first estimated by performing a bending fracture strain test. The ribbon is bent once over 180 degrees by being squeezed progressively between two parallel plates to measure the gap distance (ribbon bending diameter) at which a visible sudden rupture through the ribbon layer is occurring. The bending fracture strain is expressed bye, wherein e, =tI(D-t), t is the ribbon thickness and D is the bending diameterofthe fractured ribbon. One mustalsotake into accountthe type offracture 30 occurring at the bending radius as an additional indicator ofthe ductility. A fractureWO 2011/060546 70 PCT/CA2010/001844

can be the occurrence of a local rupture appearing somewhere along the axial bending length or, a sudden ribbon complete rupture. For a same fractured bending diameter, a ribbon rupturing completely is considered more brittle than one rupturing partially. The bending side also influences the bending fracture strain diameter. A brittle ribbon having a natural bending curve in a rest position will be more prone to fracture when bent on the opposite side of its natural curved radius as the bending stress is more intense. Ductility is also estimated with a shear cutting test. The ductility can be expressed 10 with the ability for the ribbon to be sheared cut in a straight line that follows the cutting blades. A good ductile ribbon will smoothly be cutalong the cutting linewhere both shear blade edges meet. A slightly brittle ribbon will partially rupture sideways at one or several places along the edge of the cutting line. However a very brittle ribbon will suddenly and completely rupture. Ductility is also estimated with a tearing test. Ductility can be expressed with the abilityforthe ribbon to be torn apart like doing so with a papersheet. A good ductile ribbon will smoothly be torn apart from one edge to the other, while a more brittle ribbon would be subject to sudden partial ruptures over a short distance. For a 20 significantly brittle ribbon, an immediate and complete rupture apartwill occur.
A "completely ductile" alloy ribbon according to the present invention will never rupture in all three performed tests as opposed to avery brittle alloy ribbon which will always completely and suddenly break.
Before an iron-based amorphous alloy ribbon was annealed with the apparatus of the present invention, a series of as-cast samples were submitted to each of the three tests to ensure that they were completely ductile. After the annealing treatment, a long segment of ribbon was sampled and was tested to estimate its 30 ductility. The following tables give the results forthe series ofthree ductile tests thatWO 2011/060546 71 PCT/CA2010/001844

10 were performed at normal room temperature on annealed ribbon segments sampled from each run of examples 1 to 4. Each ductility test was done 10 times. For each test, the following expressions are used to describe the ribbon physical behavior undertest. The bending fracture strain test is expressed by the 

### e, interval and also includes the type of fracture observed: foldable 

### (e, =1 with no rupture); partial rupture; and not complete rupture. The shear cut test is expressed in terms of: cuttable (smooth progressive cut with no rupture); partial rupture; and complete rupture. Lastly, the tear test result is expressed in terms of: tearable (smooth progressive tearwith no rupture); partial rupture; and complete rupture.WO 2011/060546 

### 72 PCT/CA2010/001844

Example 

### e, Foldable Partial rupture Complete rupture 

### 1 .01-1 

### 8 2 

### 0 2 

### .01-1 

### 8 2 

### 0 3 

### .01-1 4 

### 6 0 4 

### .01-1 4 

### 6 0 Table 2-Bending fracture strain test results
- opposite side to natural bending curve Example 

### e, Foldable Partial rupture Complete rupture 

### 1 1 10 0 0 2 

### 1 10 0 0 3 

### 1 10 0 0 4 

### 1 10 0 0 Table 3-Bending fracture strain test results
- same sideto natural bending curve Example Cuttable Partial rupture Complete rupture 

### 1 10 0 0 2 

### 10 0 0 3 

### 10 0 0 4 

### 10 0 0 Table 4-Shearcutting test resultsWO 2011/060546 73 PCT/CA2010/001844

Example Tearable Partial rupture Complete rupture 

### 1 2 5 

### 3 2 2 7 

### 1 

### 3 5 5 

### 0 4 

### 8 2 0 Table 5-Tearing test results
All iron-based amorphous alloy ribbons that were curved annealed with the in-line annealing apparatus of the present invention and disclosed in the cited examples show good ductility. According to the present invention, a curved annealed ribbon is considered "ductile" if it is cuttable and foldable on the same side of the natural bending curve. The curved annealed iron-based amorphous alloy ribbons in-line annealed with the apparatus of the present invention are ductile at normal room 10 temperature. The annealed ribbon coming out ofthe in-line annealing apparatus can be continuously rolled up on a mandrel to make reels of ribbon or cores and switch from reels of ribbon or cores at very high production yields. The in-line annealing apparatus of the present invention can be used to massively produce reels of annealed iron-based amorphous alloy ribbons that show excellent magnetic properties and which are acceptable for making cores for distribution transformers, HIF, pulse powercores, and otherelements. Although the treated ribbons in the cited examples are "ductile", they are not "completelyductile" compared to as-cast ribbons. This loss ofductilitystill represents 20 a small risk of breaking the ribbon after cool down during in-line annealing and after treatment during handling. Based on the fact that most iron-based amorphous alloy ribbons show a ductile-to-brittle transition at a temperature (Tdb

### O) below which they are brittle and above which they are ductile, the iron-based amorphous alloy ribbons that were annealed with the annealing apparatus of the present invention andWO 2011/060546 

### 74 PCT/CA2010/001844

disclosed in the cited examples have a ductility level which would correspond to a Tdbo which has shift-up just below normal room temperature as shown in Figure 8. Therefore, increasing the temperature of the alloy should render the ribbon more ductile. The ductilityof ribbons annealed with the apparatus ofthe present invention has been found to have a great dependency on temperature. The annealed ribbons were submerged in an oil bath heated at differenttemperatures and were submitted again to the same ductility tests. The number of observed ruptures significantly started to drop for afew degrees above the normal room temperature. Above 50°C, the numbers of ruptures were down by half. The sensitivity to the temperature was 10 so high that for temperatures at about 100°C, the 2605SA1 alloy ribbons became completely ductile according to the present performed ductile tests. For the 2605HB1, complete ductility was reached at about 80e. Therefore, the handling, rolling up and cutting of iron-based amorphous alloy ribbons that have been in-line annealed with the apparatus ofthe present invention can be done at optimal ductility just by handling the ribbon above atemperature afew tens ofdegrees over normal room temperature, preferably above 80°C for 2605HB1 and above 100°C for 2605SA1. As mostdielectric materials in transformers are irreversiblydeteriorated at temperatures above 150e, rolling up ofthe ribbon to form acore around the coils of the transformer could be achieved at a temperature up to 150e to benefit from a 20 maximum gain in ductility.
In the apparatus shown in Figure 24, a third infrared sensor 52 has been added to measure the ribbon temperature that exits the treatment apparatus. The flow of coolant through cold roller 51 can be controlled in order for the ribbon to exit the treatment apparatus at a temperature ToutO greater than normal room temperature, preferably greater than 80°C for 2605HB1 and above 100°C for 2605SA1, so that the ribbon remains optimally ductile for the following post handling operations, as shown in Figure 8. Since complete ductility is reached at a temperature dependant on the alloy composition, the handling temperature will be set accordingly. To 30 maintain the ribbon temperature during post handling, any cutting tool or guidingWO 2011/060546 

### 75 PCT/CA2010/001844

surfaces need to be kept nearthe same temperature. Once taken-up on a mandrel, the ribbon was allowed to gradually cool down to normal room temperature without anyfurtherdeterioration ofthe properties. By keeping the alloy completelyductile all along the forwarded treatment path, risk of a ribbon breakage during treatment is reduced to minimum and production yield istherefore maximized.
The flat orcurved annealed and cuttable amorphous ferromagnetic ribbon produced with the in-line annealing apparatus of the present invention applies to building of ferromagnetic cores for use in equipment such as distribution transformers, HIF, 10 pulse powercores, and otherelements. With the apparatus ofthe present invention, the in-line annealing ofthe amorphous alloy ribbon can be performed atsuch a high feeding rate that it makes-it more beneficial in term of economies of scale to locate the apparatus nextto the amorphous alloycasting system atthe alloy manufacturing plant. Because the in-line annealed ribbon remains ductile after treatment, stored ribbons in large reels around a mandrel atthe casting plant can then be shipped to the transformer manufacturer using the same methods used for shipping as-cast ribbon. The received in-line annealed reels will then be unrolled by the transformer manufacturer to be rolled again onto a mandrel located around the coils of the transformer. This eliminates all necessary equipments, associated floor space and 20 labour required for making conventional field furnace annealing rectangular-cutcores and which is normally performed atthe transformer manufacturing plant. As it is cuttable, the ribbon could also be used as a magnetic shielding foil for electronic devices, orfor making magnetoimpedance sensors, orfor making markers forarticle surveillance systems. The ribbon is flexible and can be punched into the desired shape. The form can either be circular at a given radius ra, orflat, depending ifthe ribbon has been curved orflatannealed.
A flat annealed iron-based amorphous ferromagnetic alloy 

### ribbon in-line annealed with the apparatus ofthe present invention can be used for producing stack cores. 30 Reels containing flat cuttable annealed ribbon can be unrolled and cut orpunched inWO 2011/060546


### 76 PCT/CA2010/001844

segments having a predetermined length or outline. These segments are then stacked and grouped to form cores having a predetermined shape. Stacked cores can be used in the fabrication oftransformers. However, amorphous alloy ribbons are very thin and therefore have no stiffness. To be more handleable, a group of segments can be stacked and bound with either an organic or inorganic binder to give a rigidity equivalentto athicksteel sheet. Sincethe performances ofiron-based amorphous ferromagnetic alloys such as Metglas 2605SA1 and 2605HB1 are sensitive to external applied stresses, the binder, when cured, must not introduce significant stresses on the surfaces of the ribbons which would lead to a serious 10 deterioration of magnetic performance. Furthermore, the coefficient of thermal expansion of the binder should match that of the ribbon to avoid the creation of stresses due to differential thermal expansion, which could also lead to serious deterioration of the magnetic performances. Also, a binder can be applied on a curved-in-line-annealed ribbon before it is to be rolled up to from a core to obtain a selfconsistentcore.
A curved annealed ribbon in-line annealed with the apparatus of the present invention can be used for producing circularcores. During rolling up ofthe ribbon to form acore, a minimal tensile stress must be applied to properly roll up the ribbon. A 20 high ribbon rolling up tensile stress improves the filling factor of the material in the core but introduces stresses that remain in the core once completely rolled up and which can seriouslydeterioratethe magnetic performances. Therefore, the rolling up tensile stress must be controlled to limit the residual stresses in the final formed core. Also, each rolled up layerof ribbon will have afinal bending radius according to its own radial position within the core. There will be a bending stress in each rolled up layerand its intensitywill depend on the curvature change imposed on the ribbon compared to the radius ra where maximum alleviated stresses occur. To minimize the curvature change, the innerto outer radius ofthe circular core will preferably be close to ra. More preferably, the radius r aofthe curved in-line annealed ribbon ofthe 30 present invention will be situated between the inner radius and outer radius of theWO 2011/060546 

### 77 PCT/CA2010/001844

circular formed core. More preferably, ra will be closer to the outer radius of the circular formed core as the exciting magnetic field gets weaker close to the outer peripheral portion of the core thus, benefiting of a stronger field in the inner peripheral portion of the circular core for compensating the increased force field required to magnetize the slightly deformed ribbon in the inner region of the core. However, magnetic performance of circular cores having a very thick amount of rolled up ribbon can be improved by rolling up successive quantities of ribbons each annealed at a specific radius which increases from one quantity of ribbons to the next (ra1 < ra2 < ra3

...). 

### 10 Partofthe core loss produced in astacked or rolled upferromagnetic core underan applied AC magnetic field is caused by the induced currents flowing through the inter-laminarcontacts. Increasing the frequency ofthe applied AC field will increase the inter-laminar voltages, which increase the inter-laminar currents and therefore increasethe core loss. The inter-laminarvoltages also increase with the width ofthe core. Attenuating these currents will greatly improve the magnetic performances of the core, especially at high frequency. To reduce these inter-laminar currents, it is necessary to increase the ribbon surface resistivity. With the in-line annealed amorphous alloy ribbon of the present invention, because it can be rolled-up-after20 annealing, the surface ofthe ribbon can be coated eitherwith an organicor inorganic insulating coating before it is stacked in a core. However, there is a drawback of coating the ribbon. It will affect the stacking factor of the core as the coating will occupy some space between each layer. Only one side coating is required to increase inter-laminarinsulation. On a ribbon having athickness at about25 f,Jm, the coating has to be very thin if one wants to keep a good stacking factor. For 60Hz frequency operations, applying averythin insulating coating «1 f,Jm) on the ribbon is enough to increase the inter-laminar electrical resistance and will therefore significantly improve the magnetic performances of the core, especially for wide cores. A slightly thicker insulating layer having a high dielectric strength may be 30 required for providing proper insulation in a pulse power core such as required in aWO 2011/060546 

### 78 PCT/CA2010/001844

HIF accelerator. However, coating such avery thin insulating layer requires precise control ofthe coating process.
The E-coat process, also known as Electrocoat, electrophoretic paint, EDP or electrodeposited paint, consists of applying a voltage on the conductive material to be coated when it passes is an emulsion oforganic polymers and de-ionized water. The voltage is applied between the conductive material and an auxiliary electrode submerged in the emulsion. Charged polymers within the emulsion will migrate electrophoretically to the target electrode ofthe opposite charge (the alloy ribbon), 10 become insoluble, and form the coating. The thickness of the coating depends on the applied voltage orthe submerged time. Such acoating process can be efficiently used to coat avery thin insulating layer on at least one side ofthe in-line annealed amorphous alloy ribbon ofthe present invention. A reel of ribbon is mounted on an insulated hub. The ribbon is then unrolled and plunged into an electrophoretic bath for a predetermined period of time and at a specific voltage to be coated with an organic polymer. The ribbon is then dried and rolled up again on an insulated takeup mandrel. The performances ofamorphous ferromagnetic alloys being sensitive to external applied stresses, the coating must not introduce significant stresses on the surfaces of the ribbons, which would lead to a serious deterioration of magnetic 20 performance. Furthermore, the coefficientofthermal expansion ofthe coating should match that ofthe ribbon to avoid the creation ofstresses due to differential thermal expansion which could also lead to seriousdeterioration ofmagneticperformance. Although preferred embodiments of the present invention have been described in detailed herein and illustrated in the accompanying drawings, it is to be understood that the invention is not limited to these precise embodiments and that various changes and modifications may be effected therein without departing from the scope orspiritofthe present invention.WO 2011/060546

CLAIMS: 

### 79 PCT/CA2010/001844

1. A method fortreating an amorphous alloy ribbon, comprising steps of: a) feeding forward, tensioning and guiding the amorphous alloy ribbon along a path atapresetfeeding rate; b) heating the amorphous alloy ribbon at a point along said path at a rate greaterthan 103 °C/secto atemperatureto initiate athermal treatment; c) cooling the amorphous alloy ribbon at a rate greater than 103 °C/sec until thethermal treatmentends; 10 d) applying a series of mechanical constraints on the ribbon during said thermal treatment until the amorphous alloy ribbon adopts a specific shape at rest aftersaid thermal treatment; and e) cooling the amorphous alloy ribbon ata rate to preserve said specificshape, aftersaid thermal treatment.
2. The method according to claim 1, wherein the thermal treatment is performed to maintain an amorphous state ofthe ribbon.
3. The method according to claim 1, wherein the thermal treatment is performed 20 to initiate crystallisation ofthe amorphous alloy ribbon.
4. The method according to claim 1, wherein the thermal treatment is performed to obtain partial crystallisation ofthe amorphous alloy ribbon.
5. The method according to claim 1, wherein the thermal treatment is performed to obtain full crystallisation ofthe amorphous alloy ribbon.
6. The method according to claim 1, wherein in step a), the presetfeeding rate is greaterthan 1 m/sec. 

### 30

### wo 2011/060546 

### 80 PCT/CA2010/001844

7. The method according to claim 1, wherein, in step b), the heating is done at a rate greaterthan 104oC persecond.
8. The method according to claim 1, wherein, in step c), the cooling is done at a rate greaterthan 104oC persecond.
9. The method according to anyone of claims 1 to 8, wherein the thermal treatment is performed during a period oftimethat is lessthan one second.
10 10. The method according to anyone of claims 1 to 8, wherein the thermal treatment is performed during a period of time that is less than one tenth of a second.
11. The method according to anyone of claims 1 to 10, wherein step e) cools the amorphous alloy ribbon to a handling temperature above a temperature threshold Tdbtowhich acomplete ductilityofthe amorphous alloy ribbon is obtained.
12. The method according to claim 11, wherein said handling temperature is above ambienttemperature and belowsaid temperature to initiatethe thermal treatment. 20 13. The method according to anyone ofclaims 1 to 12, wherein: in step b) the amorphous alloy ribbon is in contactwith at leastonefirst cylinder having afirst cylindrical surface located along said path; step b) further comprises a step oftensioning the amorphous alloy ribbon with respect to the first cylindrical surface to obtain a first static contact between the amorphous alloy ribbon and the first cylindrical surface, the first static contact stretching overafirst contact angle.around thefirst cylindrical surface; step b) further comprises a step of maintaining said first cylindrical surface at a temperature greaterorequal to said temperatureto initiatethe thermal treatment;

### wo 2011/060546 

### 81 PCT/CA2010/001844

10

20 in step c) the amorphous alloy ribbon is in contact with at least one second cylinderhaving asecond cylindrical surface located along said path; step c) further comprises a step oftensioning the amorphous alloy ribbon with respect to the second cylindrical surface to obtain a second static contact between the amorphous alloy ribbon and the second cylindrical surface, the second static contact stretching over a second contact angle around the second cylindrical surface; and step c) further comprises a step of maintaining said second cylindrical surface at atemperature lowerthan said temperatureto initiatethethermal treatment.
14. The method according to claim 13, wherein: in step d) the amorphous alloy ribbon is in contact with at least one third cylinder having athird cylindrical surface located along said path; step d) further comprises a step oftensioning the amorphous alloy ribbon with respect to the third cylindrical surface to obtain a third static contact between the amorphous alloy ribbon and the third cylindrical surface, the third static contact stretching overathird contact angle around thethird cylindrical surface; and step d) further comprises a step of maintaining said third cylindrical surface at said temperature to initiatethe thermal treatment.
15. The method according to claim 13 or 14, wherein the step of tensioning the amorphous alloy ribbon with respectto the cylindrical surfaces is done at atension in the range of25to 200 MPa.
16. The method according to claim 13 or 14, wherein the step of tensioning the amorphous alloy ribbon with respecttothe cylindrical surfaces is done at atension in the range of50to 100 MPa.WO 2011/060546 82 PCT/CA2010/001844

17. The method according to claim 15 or 16, wherein the step of tensioning the amorphous alloy ribbon is done to favourthe development ofa magnetic anisotropy in the ribbon.
18. The method according to claim 14, wherein the amorphous alloy ribbon is in contactwith at least one guide roller proximate a selected one ofthe first, second or third cylinders, said guide roller having a radius that is smaller than the selected cylinder and being positioned proximate both an initial contact point and a final contact point between the ribbon and the selected cylinderto maximize said contact 10 angle ofsaid selected cylinder.
19. The method according to anyone of claims 1 to 18, wherein in step d) the specificshape is curved and the method furthercomprises an additional step of: 

### f) rolling aspecificamount ofthe amorphous alloy ribbon onto a mandrel toform acore having an inner radius and an outer radius, wherein said specificshape has a radius ofcurvature selected between said inner radius and said outer radius.
20. The method according to anyone of claims 1 to 18, wherein in step d) the specific shape isflat and the method furthercomprises an additional step of: 20 

### f) cutting and stacking segments ofthe amorphous alloy ribbon.
21. The method according to anyone of claims 1 to 18, wherein in step d) the mechanical constraints change to vary a radius ofcurvature ofthe specific shape of the amorphous alloy ribbon along a length thereof, and the method furthercomprises an additional step of: 

### f) rolling said length of the amorphous alloy ribbon onto a mandrel to form a core.
22. The method according to anyone of claims 19 to 21, comprising an additional 30 step before step

### f) of:

### wo 2011/060546

83 PCT/CA2010/001844

i) coating at least one side of the amorphous alloy ribbon with a dielectric material.
23. The method according to claim 22, wherein the dielectric material is an organic dielectric material.
24. The method according to claim 22, wherein in said step i), coating is performed by means ofelectrodepositing.
10 25. The method according to claim 22, wherein said step i) further comprises steps of applying a voltage on the amorphous alloy ribbon and feed forwarding the ribbon in an emulsion oforganic polymers and de-ionized waterfora period oftime.
26. The method according to anyone of claims 19 to 21, comprising an additional step, before said stepf), of: i) coating at leastone side ofthe amorphous alloy ribbon with a binder.
27. The method according to anyone of claims 1 to 12, wherein a tension is increased or reduced along the path ofthe amorphous alloy ribbon by a tensioning 20 apparatus, said tensioning apparatus comprising: at leastone motorhaving ashaft; a circular device coupled to the shaft of the motor, said circular device having a surface making a static contact with the ribbon over an angle, the surface having astaticfriction coefficientwith respecttothe ribbon; and a controllerforcontrolling torque ofsaid motorshaftto increase or reduce a tensile stress in the amorphous ribbon.
28. The method according to claim 27, wherein said tensioning apparatus is located along said path to increase the tensile stress in the ribbon before thermal 30 treatment is initiated.

### wo 2011/060546 84 PCT/CA2010/001844

29. The method according to claim 27, wherein said tensioning apparatus is located along said path to reduce the tensile stress aftersaid thermal treatment.
30. The method according to claim 27, wherein said tensioning apparatus is located along said path for controlling the tensile stress in the ribbon during said thermal treatment.
31. The method according to anyone of claims 1 to 30, wherein the ribbon being 10 fed along the path is delivered to a target position on a structure by a guiding apparatus, said guiding apparatus comprising: - a body; - a guide roller mounted on the body, having a flat peripheral surface lined with lateral guides for supporting and guiding the ribbon, the guide roller having a receiving section for receiving the ribbon and a delivering section for delivering the ribbon atthe target position; and - a pivotfor pivotably mounting the bodyto the structure, the pivot having a pivot axis tangentially aligned with the delivering section of the roller; in operation, the body pivots with respect to the structure by means ofthe pivot so that the receiving 20 section of the roller receives the ribbon and accommodates translations thereof to delivervia said delivering section the ribbon atthe target position.
32. The method according to claim 13, wherein: in step e) the amorphous alloy ribbon is in contact with a plurality of spaced apart cooling cylinders each having a cooling cylindrical surface located along said path;step e) further comprises a step oftensioning the amorphous alloy ribbon with respect to the cooling cylindrical surfaces to obtain a cooling static contact between the moving amorphous alloy ribbon and the cooling cylindrical surfaces, the coolingWO 2011/060546 85 PCT/CA2010/001844

staticcontact stretching over respective contact angles around the cooling cylindrical surfaces; and step e) further comprises a step of maintaining said cooling cylindrical surfaces atatemperature lowerthan said temperatureto initiatethethermal treatment.
33. An iron-based amorphous alloy cast as a ribbon, heat-treated by in-line annealing at a temperature without reaching onset crystallization with heating and cooling attemperature rates greaterthan 103 °C/sec.
10 34. The iron-based amorphous alloy according to claim 33, wherein, when said ribbon is stacked or rolled upto form acore, said ribbon has a 8ao/8satthat is greater than 0.80.
35. The iron-based amorphous alloy according to claim 33, wherein the ribbon is ductile at normal room temperature and completely ductile at a temperature greater than normal room temperature
36. An iron-based amorphous alloycastas a ribbon comprising a nominal chemical composition Fea0811Sig, numbers being in atomic percent, with incidental impurities, 20 heat-treated by in-line annealing at a temperature above 450°C without reaching onset crystallization with heating and cooling at temperature rates greater than 103 DC/sec.
37. The iron-based amorphous alloy according to claim 36, wherein, when said ribbon is stacked or rolled uptoform core, the ribbon has acore loss lowerthan 0.25 W/kg at60 Hz at a magnetic induction of 1.3Tesla.
38. The iron-based amorphous alloy according to claim 36, wherein, when said ribbon is stacked or rolled up to form core, said ribbon has a 8ao that is greaterthan 30 about 1.3Tesla afterannealing.WO 2011/060546 86 PCT/CA2010/001844

39. The iron-based amorphous alloy according to claim 36, wherein, when said ribbon is stacked or rolled uptoform acore, said ribbon has a Bao/Bsatthat is greater than 0.80.
40. The iron-based amorphous alloy according to claim 36, wherein the ribbon is ductile at normal room temperature and completely ductile at atemperature greater than 100°C.
10 41. The iron-based amorphous alloy according to claim 33, comprising a nominal chemical composition FeaBbSicCd where 80<a<84, 8<b<18, 0<c:55 and 0<d:53, numbers being in atomic percent, with incidental impurities.
42. The iron-based amorphous alloy according to claim 41, wherein, when said ribbon is stacked or rolled uptoform core, the ribbon has a core loss lowerthan 0.25 W/kg at60 Hz at a magnetic induction of 1.5Tesla.
43. The iron-based amorphous alloy according to claim 41, wherein, when said ribbon is stacked or rolled up to form core, said ribbon has a BaD that is greaterthan 20 about 1.3Tesla afterannealing.
44. The iron-based amorphous alloy according to claim 41, wherein, when said ribbon is stacked or rolled up to form core, said ribbon has a BaD that is greaterthan about 1.4Tesla afterannealing.
45. The iron-based amorphous alloy according to claim 41, wherein, when said ribbon is stacked or rolled up to form core, said ribbon has a BaD that is greaterthan about 1.5Tesla afterannealing.WO 2011/060546 87 PCT/CA2010/001844

46. The iron-based amorphous alloy according to claim 41, wherein, when said ribbon is stacked or rolled uptoform a core, said ribbon has a Bso/Bsatthat is greater than 0.80.
47. The iron-based amorphous alloy according to claim 41, wherein, when said ribbon is stacked or rolled up to form a core, said ribbon has a Bso/Bsatthat is greater than 0.90.
48. The iron-based amorphous alloy according to claim 41, wherein the ribbon is 10 ductile at normal room temperature and completely ductile at atemperature greater than about 80°C.
49. The iron-based amorphous alloy according to anyone of claims 41 to 48, comprising a nominal chemical composition Fes1.8B15.sSiz.1Co.3, numbers being in atomic percent, with incidental impurities.
50. An amorphous alloy ribbon treated in accordancewith the method ofanyone of claims 1 to 32.
20 51. The amorphous alloy ribbon according to claim 50, comprising a nominal chemical composition FeaoB11Sig, numbers being in atomic percent, with incidental impurities.
52. The amorphous alloy ribbon according to claim 50, comprising a nominal chemical composition FeaBbSicCd where 80<a<84, 8<b<18,**0<c~5** and**0<d~3,** numbers being in atomic percent, with incidental impurities.
53. The amorphous alloy ribbon according to claim 52, compnslng a nominal chemical composition FeS1.8B15.SSiz.1CO.3, numbers being in atomic percent, with 30 incidental impurities.

### wo 2011/060546 88 PCT/CA2010/001844

54. A heatexchange system forexchanging heatwith an article comprising: - asupportstructure; - a heatexchangerring elementcapable ofbeing heated; - a heat diffuser ring element having an outer surface to be in contact with said article, said heat diffuser ring element having an inner surface in contact with said heatexchangerring element; and - aframe structure supporting said heatexchanger ring elementand said heat diffuser ring element, said frame structure being rotatably mounted on the 10 supportstructure.
55. The heat exchange system according to claim 54, wherein the heat exchanger ring element is a resistive element capable of being in sliding rotatable contact with an electrical powersource.
56. The heat exchange system according to claim 54, wherein the heat exchanger ring element is a resistive element, further comprising an antenna for heating by magnetic induction the heatexchanger ring element.
20 57. The heat exchange system according to anyone of claims claim 54 to 56, further comprising a slotted structure integrallyformed with the heat exchanger ring element and laterally surrounding said heat exchanger ring element, the slotted structure having slots extending transversallyto the heatexchangerring element.
58. The heat exchange system according to anyone of claims claim 54 to 57, wherein the heat exchanger ring element is made of stainless steel and the heat diffuser ring element is made of copper and mounted by electrodeposition on the heatexchanger ring element.
30 59. Asystem fortreating an amorphous alloy ribbon, comprising:WO 2011/060546 

### 89 PCT/CA2010/001844

- a moving device for feeding forward, tensioning and guiding the amorphous alloy ribbon along a path ata presetfeeding rate; - a heating system for heating the amorphous alloy ribbon at a point along said path at a rate greater than 103 °C/sec to a temperature to initiate a thermal treatment; - a first cooling system cooling the amorphous alloy ribbon at a rate greater than 103 °C/sec until the thermal treatmentends; - a mechanical constraint application deviceforapplying aseries ofmechanical constraints on the ribbon during said thermal treatment until the amorphous alloy 10 ribbon adopts aspecificshape at restaftersaid thermal treatment; and - a second cooling system for cooling the amorphous alloy ribbon at a rate to preserve said specificshape, aftersaid thermal treatment.
60. The system according to claim 59, wherein the heating system and the first cooling system are set so that the thermal treatment is performed to maintain an amorphous state ofthe ribbon.
61. The system according to claim 59, wherein the heating system and the first cooling system are set so that the thermal treatment is performed to initiate 20 crystallisation ofthe amorphous alloy ribbon.
62. The system according to claim 59, wherein the heating system and the first cooling system are set so that the thermal treatment is performed to obtain partial crystallisation ofthe amorphous alloy ribbon.
63. The system according to claim 59, wherein the heating system and the first cooling system are set so that the thermal treatment is performed to obtain full crystallisation ofthe amorphous alloy ribbon.WO 2011/060546 

### 90 PCT/CA2010/001844

64. The system according to claim 59, wherein the preset feeding rate of the moving device is greaterthan 1 m/sec.
65. The system according to claim 59, wherein the heating system heats at a rate greaterthan 104oCpersecond.
66. The system according to claim 59, wherein the first cooling system cools at a rate greaterthan 104oCpersecond.
10 67. The system according to anyone of claims 59 to 66, wherein the heating system and the first cooling system are set so that the thermal treatment is performed during aperiod oftimethat is lessthan one second.
68. The system according to anyone of claims 59 to 66, wherein the heating system and the first cooling system are set so that the thermal treatment is performed during aperiod oftimethat is less than onetenth ofasecond.
69. The system according to anyone of claims 59 to 68, wherein the second cooling system cools the amorphous alloy ribbon to a handling temperature above a 20 temperature threshold Tdb that is sufficient to obtain complete ductility of the amorphous alloy ribbon.
70. The system according to claim 69, wherein said handling temperature is above ambienttemperature and belowsaid temperatureto initiatethe thermal treatment.
71. The system according to anyone of claims 59 to 70, wherein the heating system comprises at least one first cylinder in contact with the amorphous alloy ribbon, said at least one first cylinder having afirst cylindrical surface located along said path, the system further comprising a first tensioning apparatus for tensioning 30 the amorphous alloy ribbon with respecttothefirst cylindrical surface to obtain afirstWO 2011/060546

91 PCT/CA2010/001844

static contact between the amorphous alloy ribbon and the first cylindrical surface, the first static contact stretching over afirst contact angle around the first cylindrical surface, a temperature of said first cylindrical surface being maintained at a temperature greater or equal to said temperature to initiate the thermal treatment, the first cooling system comprises at least one second cylinder in contact with the amorphous alloy ribbon, said at least one second cylinder having a second cylindrical surface located along said path, the system further comprising a second tensioning apparatus for tensioning the amorphous alloy ribbon with respect to the second cylindrical surface to obtain a second static contact between the amorphous 10 alloy ribbon and the second cylindrical surface, the second static contact stretching overa second contact angle around the second cylindrical surface, atemperature of said second cylindrical surface being maintained at a temperature lower than said temperature to initiatethe thermal treatment.
72. The system according to claim 71, wherein the mechanical constraint application device comprises in contact with the amorphous alloy ribbon, said at least one third cylinder having athird cylindrical surface located along said path, the system further comprising a third tensioning device for tensioning the amorphous alloy ribbon with respectto the third cylindrical surface to obtain athird staticcontact 20 between the amorphous alloy ribbon and the third cylindrical surface, the third static contact stretching over a third contact angle around the third cylindrical surface, a temperature ofsaid third cylindrical surface being maintained at said temperature to initiatethethermal treatment.
73. The system according to claim 71 or 72, wherein the tensioning apparatuses tension the amorphous alloy ribbon with respect to the cylindrical surfaces at a tension in the range of25 to 200 MPa.WO 2011/060546 92 PCT/CA2010/001844

74. The system according to claim 71 or 72 wherein the tensioning apparatuses tension the amorphous alloy ribbon with respect to the cylindrical surfaces at a tension in the range of50to 100 MPa.
75. The system according to claim 73 or 74, wherein the tensioning apparatuses tension the amorphous alloy ribbon to favour the development of a magnetic anisotropy in the ribbon.
76. The system according to claim 72, furthercomprising at leastone guide rollerto 10 which the amorphous alloy ribbon is in contact, proximate aselected one ofthe first, second or third cylinders, said guide roller having a radius that is smaller than the one ofthe selected cylinders and being positioned proximate both an initial contact point and a final contact point between the ribbon and the selected cylinder to maximize said contactangle ofsaid selected cylinder.

77. The system according to anyone of claims 59 to 76, further comprising a mandrel onto which a specific amount of the amorphous alloy ribbon is rolled up, said mandrel having an inner radius and an outer radius, said specific shape having a radius ofcurvature selected between said inner radius and said outer radius. 

### 20 78. The system according to anyone ofclaims 59 to 76, furthercomprising acutter and stacking device for cutting and stacking segments of the amorphous alloy ribbon.
79. The system according to anyone of claims 59 to 76, wherein the mechanical constraint application device apply constraints to vary a radius of curvature of the specific shape ofthe amorphous alloy ribbon along a length thereof, and the system further comprises a mandrel onto which a specific amount of the amorphous alloy ribbon is rolled up. 

### 30WO 2011/060546 93 PCT/CA2010/001844

80. The system according to anyone of claims 77 to 79, further comprising a coating system for coating at least one side of the amorphous alloy ribbon with a dielectricmaterial.
81. The system according to claim 80, wherein the dielectric material is an organic dielectricmaterial.
82. The system according to claim 80, wherein the coating system is an electrodepositing system. 10 83. The system according to claim 80, further comprising a voltage application device for applying a voltage on the amorphous alloy ribbon, and a bath system comprising an emulsion oforganic polymers and de-ionized waterthrough which the ribbon isfed forward fora period oftime.
84. The system according to anyone of claims 80 to 83, further comprising a binderapplication system for coating at leastone side ofthe amorphous alloy ribbon with abinder.
20 85. The system according to anyone of claims 59 to 70, further comprising a tensioning apparatus for increasing or reducing a tension in the amorphous alloy ribbon along the path, ,said tensioning apparatus comprising: at leastone motorhaving ashaft; - a circular coupled to the shaft of the motor, said circular device having a surface making a static contact with the ribbon over an angle, the surface having astaticfriction coefficientwith respecttothe ribbon; and acontrollerfor controlling torque ofsaid motorshaftto increase or reduce a tensile stress in the amorphous ribbon.WO 2011/060546



### 94 PCT/CA2010/001844

86. The system according to claim 85, wherein said tensioning apparatus is located along said path to increase the tensile stress in the ribbon before thermal treatment is initiated.
87. The system according to claim 85, wherein said tensioning apparatus is located along said path to reducethe tensile stress aftersaid thermal treatment.
88. The method according to claim 85, wherein said tensioning apparatus is located along said path for controlling the tensile stress in the ribbon during said 10 thermal treatment.
89. The system according to anyone of claims 59 to 88, further comprising a guiding apparatus for delivering the ribbon to a target position on a structure, said guiding apparatus comprising: - abody; - a guide roller mounted on the body, having aflat peripheral surface lined with lateral guides for supporting and guiding the ribbon, the guide roller having a receiving section for receiving the ribbon and a delivering section for delivering the ribbon atthetarget position; and 20 - a pivotfor pivotably mounting the bodyto the structure, the pivot having a pivot axis tangentially aligned with the delivering section of the roller, in operation, the body pivots with respect to the structure by means ofthe pivot so that the receiving section of the roller receives the ribbon and accommodates translations thereof to delivervia said delivering section the ribbon atthetarget position.
90. The system according to claim 72, wherein the second cooling system comprises a pluralityofspaced apartcooling cylinders in contactwith the amorphous alloy ribbon, said spaced apart cooling cylinders each having a cooling cylindrical surface located along said path, the system further comprising atensioning system 30 for tensioning the amorphous alloy ribbon with respect to the cooling cylindricalWO 2011/060546 

### 95 PCT/CA2010/001844

surfaces to obtain a cooling static contact between the moving amorphous alloy ribbon and the cooling cylindrical surfaces, the cooling static contact stretching over respective contact angles around the cooling cylindrical surfaces, a temperature of said cooling cylindrical surfaces being maintained at a temperature lowerthan said temperature to initiatethe thermal treatment.WO 2011/060546 PCT/CA2010/001844



### 1/24
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SUBSTITUTE SHEET (RULE 26)INTERNATIONAL SEARCHREPORT

A CLASSIFICATIONOF SUBJECTMATTER IPC: C21]) 9/573 (2006.01), C21]) 1/42 (2006.01) C22C45/02 (2006.01) AccordingtoInternationalPatentClassification(IPC)ortobothnationalclassificationandIPC
B. FIELDS SEARCHED Minimumdocumentation searched (classification systemfollowed byclassificationsymbols) IPC: C21]) 9/573 (2006.01), C21]) 1/42 (2006.01) C22C45/02 (2006.01) International applicationNo. PCT/CA2010/001844

Documentationsearchedotherthanminimumdocumentationto theextentthatsuchdocuments areincludedinthefields searched

Electronicdatabase(s)consulted during theinternational search(nameofdatabase(s) and, wherepracticable, searchtermsused) TotalPatent. CanadianDatabase. ScienceDirectandACS Publication. Keywords: amorphous, Iron, alloy,ribbon,rate, crystallisation, tensile, coat,magneticcore, annealmg, transformer, FesoBIlSi9, Fea BbSl"Cct C DOCUMENTS CONSIDEREDTOBERELEVANT CategOlY* 

### x

A

A

A A Citationofdocument, withindication, whereappropriate, oftherelevantpassages US 5,069,428 (Li et a1.) 03 December 1991 (03-12-1991) *wholedocument* A NewAlethodfc)f'StressRelievingAmOlphollsAllovtoImproveAlagnetic Properties, byTaub, IEEETransactionsofMagnetics, VoL MAG-20, NO.4, JULY 1984,Page 564-570. *citedbytheapplicant* E.!lect(?ltheannealingtemperatureonmagneticproperty.fin'**tran~fimner** with amOl]7holls core, byHsu etaL, IMCAS 2009Proceedingsofthe 8thWSEAS internationalconferenceonInstrumentation, measurement, circuitsand systems, Page 171-175. *citedbytheapplicant* CA2,279,981 Al (Liebermann)06August 1998 (06-08-1995) US 4,288,260 (Sermoeta1.)08 September 1981 (08-09-1981) Relevantto claimNo. 54-58

1-53 and 59-90

1-53 and 59-90

1-53 and 59-90 1-53 and 59-90
[Xl Furtherdocuments arelisted inthecontinuationofBoxC. Specialcategoriesofciteddocmnents ")"." dOCUlllt:;l1tde±1ningthegeneralstateofthe 3rtwhichisnotconsidered tobe ofpartIcularrele,\Tance "E" earlierapplicationorpatentbutpublishedonorat1erthe international fil111g date ''L'' document,"'hichmaythrmvdoubts onpriorityclaim(s) or,'.'hichis cltedtoestabhshthepubhcatrondate ofanothercltatlonorother specwlreason(as specdied) documentreferringto anoraldisclosure, use, exhibitionorothermeans "p" documentpublishedpriorto the internationalfiling datebutlaterthan thepnont:vdate claImed Dateofthe actualcompletionoftheinternational search 26.Tanuary2011 (26-01-2011) Name andmailingaddress oftheISAICA CanadiallhltellectualPropertyOtlice PlaceduPortageI, C114- 1stFloor,BoxPCT 50Victoria Street Gatineau, QuebecKIAOC9 FacsimileNo. 001-819-953-2476 FormPCTIISAl210 (second sheet) (July2009) [X] Seepatenttinnilyalmex. "T" laterdocmnentpublisheda±1erthe internationalfiling dateorpriority date andnot111con111ct"\'liththeapl)hcattonbutclteatounderstand

- thepnnciple ortheorylUlderlymgtlelll\ientIon C"X" documentofparticularrelevance', theclaimedinventioncmIDotbe conSIderednovelorcannotbeconslderedto 111volvean 111ventlve step "1;vhenthedoclUl1entis takenalone '.y.. docmnentofpartIcularrelevance. theclallned111ventlOnemmotbe conSIderedtoIl1\/Olve an111\ientr\'e stepyvhenthedocumentlS comb111edYVlthoneormoreothersuchdocuments, suchcombination beingobviousto apersonskilledinthe art "&" documentmemberofthe samepatentfamily
Dateofmailingoftheinternational searchreport 25 Febmary2011 (25-02-2011) Authorizedotlicer PatrickMamputu (819) 994-9537

Page 3of5INTERNATIONALSEARCHREPORT InternationalapplicationNo. PCT/CA2010/001844 BoxNo. II Observationswherecertainclaimswerefoundunsearchable(Continuationofitem2ofthefirst sheet) ThisinternationalsearchreporthasnotbeenestablishedinrespectofcertainclaimsunderAliicle 17(2)(a)forthefollowing reasons: 1. [ ] ClaimNos
.. becausetheyrelateto subjectmatternotrequiredtobe searchedbythisAuthority,namely:

2 [] ClaimNos
.. becausetheyrelatetopartsoftheinternationalapplicationthatdonotcomplywiththeprescribedrequirementsto suchanextent thatnomeaningfulinternational searchcanbecarriedout, specifically'

3. [ ] ClaimNos. becausetheyaredependentclaims and arenotdrafted inaccordancewiththe secondandthird sentencesofRule6.4(a).

BoxNo. III Obserrations whereunityofinventionis lacking (Continuationofitem3 offirst sheet) ThisInternational SearchingAuthorityfoundmultipleinventions inthisinternationalapplication, as follows: Group A Claims 1-53 and 59-90 Amethod and asystemforcontinuouslyin-lineproducingamagneticcore, fi'om atreatedductile amorphous alloyribbon, tensionedand guidedalongapathatarate greaterthan [03 °C/ser. Group B Claims 54-58 Aheatexchange systemforexchangingheatwithanarticle.
[ ] As allrequired additIOnal searchfees weretimelypaidbytheapplicant, this mternational searchreportcovers all searchableclmms. 2. [X] As all searchableclaimscould be searchedwithouteffortjustifyingadditionalfees, thisAuthoritydidnotinvite paymentofadditionalfees.
3. [ ] Asonlysomeoftherequired additional searchfees weretimelypaid bytheapplicant, thisinternational searchreport coversonlythoseclmmsforwhichfees werepaid, specificallyclaimNos
..

4. [ ] Norequired additional searchfees weretimelypaidbytheapplicant. Consequently, this international searchreportis restricted to theinventionfirstmentionedintheclaims: itiscovered byclaimNos.

RemarkonProtest [ ] Theadditional searchfees wereaccompanied bythe applicant'sprotestand, whereapplicable, thepaymentofaprotestfee. [ ] Theadditional searchfees wereaccompanied bythe applicant'sprotestbutthe applicableprotest fee wasnotpaid withinthetimelimitspecifiedintheinvitation. [ ] Noprotestaccompamedthepaymentofadditional searchfees. FormPCTIISAl210 (contmuatwnoffirstsheet (2» (July2009) Page201'5INTERNATIONAL SEARCHREPORT InternationalapplicationNo. PCT/CA2010/001844
C(Continuation) DOCUMENTS CONSIDEREDTOBERELEVANT Category* Citationofdocument, withindication, whereappropriate, oftherelevantpassages RelevanttoclaimNo. A US 5,494,534 (Leu) 27 Februmy 1996 (27-02-1996) 1-53 and 59-90 A US 4,053,331 (Graham, Jr, etaL) 11 October 1977 (11-10-1977) 1-53 and 59-90

FormPCTIISAl210 (contllluatlOnofsecond sheet) (July2(09) Page4ot5Patent Document Cited in Search ReportINTERNATIONAL SEARCHREPORT Informationonpatentfamilymembers

Publication Date Patent Family Member(s) InternationalapplicationNo. PCT/CA2010/001844

Publication Date
US5069428A 03 December 1991 (03-12-1991) None
CA2279981A1 06August 1998 (06-08-1998) AU6052898A BR9807979A CN1252106A CN1234885C EP0970257A1 JP2001510508T US5873954A W09833945A1 25August 1998 (25-08-1998) 15 February2000 (15-02-2000) 03 May2000 (03-05-2000) 04January2006 (04-01-2006) 12January2000 (12-01-2000) 31 July2001 (31-07-2001) 23 February 1999 (23-02-1999) 06August 1998 (06-08-1998)
US4288260A

US4053331A
US5494534A 08 September 1981 (08-09-1981)JP54083622A JP59034780B JP1257859C
11 October 1977 (11-10-1977) None
27 February 1996 (27-02-1996) None 03July 1979 (03-07-1979) 24August 1984 (24-08-1984) 29 March 1985 (29-03-1985)

FormPCTIISAl2l0 (patentfamIlymmex) (July2009) Page501'5