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WO2015089579A1 - Matériau magnétique pour chauffage - Google Patents

Matériau magnétique pour chauffage Download PDF

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Publication number
WO2015089579A1
WO2015089579A1 PCT/AU2014/050423 AU2014050423W WO2015089579A1 WO 2015089579 A1 WO2015089579 A1 WO 2015089579A1 AU 2014050423 W AU2014050423 W AU 2014050423W WO 2015089579 A1 WO2015089579 A1 WO 2015089579A1
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Prior art keywords
ferromagnetic material
magnetic field
magnetic
ferromagnetic
order
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PCT/AU2014/050423
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English (en)
Inventor
Kiyonori Suzuki
Cordelia SELOMULYA
Mohammad Reza BARATI
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Monash University
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Monash University
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Filing date
Publication date
Priority claimed from AU2013905012A external-priority patent/AU2013905012A0/en
Application filed by Monash University filed Critical Monash University
Publication of WO2015089579A1 publication Critical patent/WO2015089579A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00—Electrotherapy; Circuits therefor
    • A61N1/40—Applying electric fields by inductive or capacitive coupling ; Applying radio-frequency signals
    • A61N1/403—Applying electric fields by inductive or capacitive coupling ; Applying radio-frequency signals for thermotherapy, e.g. hyperthermia
    • A61N1/406—Applying electric fields by inductive or capacitive coupling ; Applying radio-frequency signals for thermotherapy, e.g. hyperthermia using implantable thermoseeds or injected particles for localized hyperthermia
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
    • A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy

Definitions

  • the present disclosure relates to magnetic materials and remote heating using magnetic, materials.
  • Magnetic materials such as superparamagnetic materials (e.g., magnetite nanoparticles) and magnetic materials exhibiting a second-order magnetic transition (e.g., metallic Iron and fenites) have been used for remote heating.
  • a magnetic field is applied to the magnetic material which induces heat output from the magnetic material.
  • the present disclosure provides a magnetic heating system comprising:
  • a magnetic field generator adapted to apply an alternating magnetic field to the ferromagnetic material to induce heat emission from the ferromagnetic material.
  • the present disclosure provides a method of heating comprising:
  • a heating system and method according to the present disclosure can provide a substantially stronger heating effect than existing arrangements by utilising an extraordinary magnetic transition process known as the first-order magnetic transition.
  • the ferromagnetic material of the present disclosure exhibits a first-order magnetic transition and this is accompanied by an abrupt change in the spontaneous magnet ization. This abrupt change provides a significantly enhanced heating effect just below the magnetic transition temperature, also known as the Curie temperature ⁇ 3 ⁇ 4), which temperature may be selected or tuned depending on desired heating purposes,
  • the ferromagnetic material of the present disclosure may provide heating power of at least an order of magnitude greater than current materials used for magnetic heating.
  • the magnetic heating system and method may be configured to provide medical treatment.
  • the magnetic material may be provided in an implant and/or in the form of nanoparti.cles, and may be located, by injection or other implantation procedure, within a human or animal body.
  • heat output from the magnetic material can be controlled remotely, from a position external to the body, in some embodiments, the beat is used to provide a therapeutic effect
  • the system, and method may be adapted to provide hyperthermia therapy, which can be used to treat cancer.
  • the ferromagnetic material can be injected int or implanted in or adjacent a tumour.
  • the surrounding tumour tissue is heated by the ferromagnetic material, killing tumour cells without substantial damage- to healthy tissue.
  • the magnetic material may be adapted to provide for heating above body temperature. Heating cancer cells t a temperature above body temperature, e.g. a temperature greater than 40°C, can cause cell damage or apoptosis.
  • the temperature to which tissue or other medium are heated can be substantially dependent on the Curie temperat ure of the ferromagnetic material.
  • the Curie temperature of the ferromagnetic material may therefore be selected to be greater' than 40°C.
  • th feiTOmagnetie material may be selected to have one of a variety o different Curie Temperatures.
  • the Curie Temperature may be between 20 and 80°C, 40 and 60 : 'C, 40 and 50°G or otherwise.
  • the Curie temperature of the ferromagnetic material is 46.1°C
  • Embodiments of the present disclosure are not necessarily limited to medical use. They can have applications in an field where remote heating is desirable. A one example, they may be used in heat assisted forward osmosis water desalination technology.
  • the magnetic field generator can be adapted to apply an alternating magnetic field having an effective field strength in the order of 10 9 A/(ms),
  • the magnetic field generator may be adapted to apply an alternating magnetic field having an effective field strength of from about 4.85 x 10 s A (ms) to about 5 x lO 9 A/(ms).
  • the substantially high heating power of the ferromagnetic material can mean medical treatment is less invasive, since lower applied magnetic field strength may be required, to achieve a desired heating effect.
  • an injectable composition comprising ferromagnetic material exhibiting a first-order magnetic transition.
  • an implant comprising ferromagnetic material exhibiting a first-order magnetic transition.
  • ferromagnetic material exhibiting a first-order magnetic transition in a method of medical treatment.
  • any ferromagnetic material that exhibits a first-order magnetic transition, and which, can undergo magnetic transition at a temperature similar to a temperature at which heating is desired may be used.
  • the ferromagnetic material may be a La-Fe-Si based material.
  • the ferromagnetic material may be a compound havi ng the formula La(Fe,Si)rj.
  • the ferromagnetic material may be a Mn-Fe- P based material.
  • the ferromagnetic material may be a compound having the formula MnFej, s Co x Pi_ y Ge j ,, As a further example, the ferromagnetic materia! may he a Mn-As-Sb based material. The ferromagnetic material may be a compound having the formula MnAsi -x .Sh x .
  • a hydrogenation: or dehydrogenation process may be used to tune the Curie temperature.
  • the ferromagnetic material may therefore be a hydrided compound having the formula La(Fe,Si)r,Hy,
  • y may be between 1.4 and 2.4, between 1.6 and 2.0, equal to or above 1.7, between 1.7 and 2.0, between 1.7 and 1.9, between 1.7 and 1.8 or about 1 ,75, for example.
  • a compound of the formula La(Fe,Si)i3Hi.75 exhibits a curie temperature of 46.1°C, which may be particularly suitable for hyperthermia therapy, for example.
  • Fig- i shows the relationship between the magnetic polarisation (M) of a ferromagnetic material avid a statically applied magnetic field (H);
  • Fig. 2 shows temperature dependence of spontaneous magnetisation of second-order ferromagnetic material and represents the mechanism of self-controlled heating
  • Fig, 3 shows temperature dependence of spontaneous magnetisation of first-order ferromagnetic, material and represents the mechanism of self-control ted heating
  • Fig. 4 shows static hysteresis loss for a first-order: ferromagnetic material over temperature, and also magnetisation of the first-order ferromagnetic material over temperatures (inset);
  • f3 ⁇ 4- 5 shows temperature over time of water containing pul verised first-orde ferromagnetic material under an applied alternating magnetic field
  • Fig. 6 shows specific heat absorption rates of different magnetic samples at different magnetic field strengths
  • Fig. 7a shows temperature dependence of magnetisation for Fc-tuned La Fe,Si)j3 compounds and Fig. 7b shows the relationship between the Curie temperature and the hydrogen concentration ⁇ ⁇ ). for LaFen.37Sii.43Hy.
  • Figs, 8a and 8b illustrate a heating system configured to provide hyperthermia therapy according to an embodiment of the present disclosure
  • Figs, 9a and 9b illustrate a heating system configured to provide hyperthermia therapy according to another embodiment of the present disclosure.
  • Fig. 10 shows a relationship between the magnetic polarisation (M) of first order ferromagnetic material and a statically applied magnetic field (H) at various different in easure ment temperatures ,
  • Ferromagnetic materials exhibiting a first-order magnetic transition have a. large isothermal entrop change (AS) or adiabatie temperature change induced by a pseudo-static magnetic field. This is known as the magnetocatoric effect.
  • AS isothermal entrop change
  • adiabatie temperature change induced by a pseudo-static magnetic field This is known as the magnetocatoric effect.
  • the inventors have determined that these materials can be particularly useful in heating applications, and irreversible heating power of these materials can be enhanced dramatically by exposure to alternating magnetic fields.
  • These ferromagnetic materials can be particularly advantageous for use in medical treatment, such as hyperthermia treatment, al though they can have applications in other fields where heating is desired, such as a heat assisted forward osmosis water desalination technology.
  • Fig. .1 shows schematically the relationship between the magnetic polarisation (M) of a ferromagnetic material and a statically applied magnetic field (H).
  • the magnetic polarisation shows a tendency to increase with increasing applied magnetic field; however, the M value is saturated at H - 3 ⁇ 4 the anisotropy field.
  • the reverse magnetic field to depolarise the magnetisation from. M, to zer is defined by the coercivity (HJ.
  • the coercivity is. known to be highly dependent on the grain size in the nanoscale regime because the magnetic correlation length of material ' s is usually between 10 and 100 nm.
  • the M-H curve of superparamagnetic material does not exhibit any hysteresis beha viour under a static magnetisation process.
  • the primary cause of the heating effect in superparamagnetic particles is the relaxation behaviour of the magnetisation direction in particles which result in a certain phase shift between the alternating l!ai ⁇ ⁇ ( ⁇ ) signals,
  • embodiments of the present disclosure utilise a ferromagnetic material to which an alternating magnetic field is applied. While a loss mechanism as described above with reference to Fig. 1 is therefore applicable, it is not the onl loss mechanism. Since magnetisation polarisation is induced by the change in the magnetic domain configurations which is -time dependent, the response of the magnetic polarisation, to external alternating magnetic field shows a finite time delay due to the domain relaxation process. This delay causes a certain phase shift between Hit) and ⁇ ⁇ ( ⁇ ) which C be described b a complex magnetic permeability ; the power lass is related to the imaginary part of the permeability.
  • the area inside the M-H loop under an alternating magnetic field is far larger than under a static field.
  • This effect is significant at high frequencies and the power loss per cycle can be enhanced by 2 order of magnitude in the kHz range in some soft magnetic materials, for example. Heating power of magnetic materials may therefore be enhanced dramatically by increasin the dri ving frequency.
  • ferromagnetic materials allow for self-controlled heating.
  • ferromagnetic materials can self-regulate heating power closer to the Curie temperature (7c). This offers a considerable advantage over heating by superparamagnetic particles with which the temperature is controlled by adjusting the applied field strength.
  • ferromagnetic material is represented in Fig, 2, in which the temperature dependence of the spontaneous magnetisation- of the ferromagnetic material is shown schematically.
  • the spon taneous magnetisation (M s ) is given by the vector sum of the atomic magnetic moment
  • Target' heating power can. be realised at desired temperatures, e.g.
  • ferromagnetic materials according to the present disclosure exhibiting first-order magnetic transition, have a temperature dependence for M s near T that does not follow the Brilloum function.
  • One example of such ferromagnetic material according to the present disclosure is a La(Fe,Si)i;? compound.
  • Fig, 3 shows schematically the temperature dependence of M s for a ferromagnetic material with the first-order magnetic transition at T .
  • both ferromagnetic and paramagnetic phases may coexist in the 1 st order materials near Tc (Fig. 3) and the abrupt decrease of M s is governed by the nucleation-and-growth process of the paramagnetic phase in the ferromagnetic matrix rather than the molecular field in the ferromagnetic phase.
  • the decrease in the spontaneous magnetisation near T can be very abrupt.
  • La(Fe,Si) ' i3 has a very steep change of M s due to the presence of such a first-order magnetic transition.
  • ferromagnetic materials exhibiting first-order magnetic transition can offer considerable advantages ' as a medium for self-controlled isothermal heating, e.g. for use in medical treatment, and have determined that considerable benefits can be achieved through the application of an altern ting magnetic field to the ferromagnetic material to induce heating.
  • a melt-spun La-Fe-Si based sample was prepared and tuned by hydragenation. such that it had a T value of 46.1°C (The La-Fe-Si compound had the formula LaFe-n «7811. 3-111 , 75 in this instance.) p of 46. C was. calculated through measurement of magnetisation over a range of temperatures, as shown in the inset of Fig. 4.
  • M-H curves of a rate of 1.6 x 1.0 "3 K s, at different measurement temperatures, are shown in Fig. 10.
  • the 1 st order magnetic transition is reflected in .the shape of the M-H. curves.
  • Fig. 4 also shows the static hysteresis loss for the ferromagnetic material, over a temperature measurement range including and extending beyond the range shown, in. Fig. 1.0.
  • the hysteresis loss shows a tendency to decrease gradually as temperature increases towards ?c because both the spontaneous magnetisation and the intrinsic coereivity normally have negative temperature dependence.
  • the hysteresis loss of the sample exhibited an increase in a temperature range of between 42 and 46°C as indicated above and a particularly dramatic increase (by about 800 ) in a very narrow temperature range of between 44 and 46 6 C
  • This anomalous behaviour had not previously been recognised and the inventors recognised that the dramatic ' increase of the hysteresis loss indicated that the heating power of this first-order ferromagnetic material could be even greater unde the application of alternating magnetic field, in. consideration of higher dynamic loss that would be induced.
  • Implam H(k. ⁇ n) Frequency H.fixVf) Conceniriition SAR (W/gr)
  • La(Fe,Si)i 3 Hi.75 with a Tc of 46.1 °C has been discussed above, this Tc value being considered as potentially ideal for hyperthermia therapy application, in other embodiments: La(Fe,Si)i3 Hi 73 with different ratios of Fe and Si and/or with different Tctn y be used, e,g. depending on the desired heating temperatures (e.g. the desired therapeutic temperatures) or otherwise,
  • the selected T e may be between 20 and 80°C, 40 and 60°C, 40 and 50°C or otherwise.
  • y may be between 1.4 and 2,4, between 1.6 and 2.0, equal to or above 1.7, between 1.7 and 2.0, betwee 1.7 and 1.9, between 1.7 and 1.8 or about 1.75.
  • Other ferromagnetic compounds that are ' not based on La-Si- Fe, but which also exhibit a first-order magnetic transition, may be employed in embodiments of the present disclosure.
  • the ferromagnetic material may be a Mn-Fe-P based material, for example, having the formula MnFei. x Co x Pi. y Gey.
  • the ferromagnetic material may be a Mn-As-Sb based material having the formula MnAsi-xSb*.
  • These first-order ferromagnetic materials have 7c in the ranges extending from about 176K to 323K n the case of MnFei- x Co x Pj. y Gc y (E. Brack et al, ScriptaMaterialia 67 (20.12) 590-593) and from about 280 K. to 320 in the case of M As ⁇ Sb, (H. Wcu!a, Y. Tan be, Appl. Phys. Lett. 2001, 79, 3302). These temperature ranges are considered suitable for a variety of different applications including hyperthermia therapy, for example..
  • a heating system configured to provide hyperthermia therapy according to an embodiment of the present disclosure is illustrated in Figs. 8a and 8b.
  • the heating system includes ferromagnetic material 1 exhibiting a first-order magnetic transition and. having a Curie temperature of between 40 and 50°C, the ferromagnetic material being provided in nanoparticulate .forrn.
  • the nanoparticles 1 are injected using a syringe 6 into a cancerous tumour 2 of a subject 3.
  • a magnetic field generator 4 is arranged t apply an alternating magnetic field 5 from a remote location to the ferromagnetic material inside the tumour 2, causing apoptosis of the cancerous cells.
  • FIGs. 9a and 9b A heating system according to another embodiment of the present disclosure is illustrated in Figs. 9a and 9b.
  • the heating system includes ferromagnetic material 10 exhibiting a first-order magnetic transition and having a Curie temperature of between 40 and 50°C, the ferromagnetic material being provided in the form of aft implant.
  • the ferromagnetic implant 10 is surgically implanted into a cancerous tumour 20 of a subject 30.
  • a magnetic field generator 40 is arranged to apply an alternating magnetic field 50 from a remote location to the ferromagnetic material inside th tumour 20, causing apoptosis of the cancerous cells.
  • the feiTomagnetic material may be employed for remote heating in other technologies.
  • magnetic field-induced heating can be used to recover water from swollen hydrogel draw agents.
  • Razmjou et at. End. Sci, TecbnoL 2013, 47, 6297-6305
  • fast deswelling of polymer hydrogel particles was achieved by incorporating magnetic- y-Fe2 ⁇ 3 ⁇ 4 nanoparticles exhibiting a second-order magnetic transition.
  • the technique described in Razmjou et al., which is incorporated by reference herein, m y be further enhanced through, use of ferromagnetic materials exhibiting a First-order transition as disclosed herein,

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  • Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
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  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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Abstract

La présente invention concerne un système de chauffage magnétique comprenant un matériau ferromagnétique qui présente une transition magnétique du premier ordre et un générateur de champ magnétique adapté pour appliquer un champ magnétique alternatif au matériau ferromagnétique pour induire une émission de chaleur depuis le matériau ferromagnétique. La transition magnétique de premier ordre est accompagnée d'un changement brusque de la magnétisation spontanée. Ce changement brusque produit un effet de chauffage significativement renforcé juste au-dessous de la température de transition magnétique, ladite température pouvant être sélectionnée ou ajustée suivant les applications de chauffage souhaitées telles qu'une thérapie par hyperthermie.
PCT/AU2014/050423 2013-12-20 2014-12-16 Matériau magnétique pour chauffage Ceased WO2015089579A1 (fr)

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AU2013905012A AU2013905012A0 (en) 2013-12-20 Magnetic material for heating
AU2013905012 2013-12-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017062565A1 (fr) * 2015-10-07 2017-04-13 Boston Scientific Scimed, Inc. Mélange de nanoparticules magnétiques de lafesih avec différentes températures de curie pour améliorer l'efficacité de chauffage par induction pour l'hyperthermie thérapeutique

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110070620A1 (en) * 2009-09-21 2011-03-24 Basf Se Substrates comprising switchable ferromagnetic nanoparticles

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110070620A1 (en) * 2009-09-21 2011-03-24 Basf Se Substrates comprising switchable ferromagnetic nanoparticles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
M. KRAUTZ ET AL.: "Reversible solid-state hydrogen-pump driven by magnetostructural transformation in the prototype system La(Fe,Si)13Hy", JOURNAL OF APPLIED PHYSICS, vol. 112, 2012, pages 083918-1 - 083918-6 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017062565A1 (fr) * 2015-10-07 2017-04-13 Boston Scientific Scimed, Inc. Mélange de nanoparticules magnétiques de lafesih avec différentes températures de curie pour améliorer l'efficacité de chauffage par induction pour l'hyperthermie thérapeutique
US20170100603A1 (en) * 2015-10-07 2017-04-13 Boston Scientific Scimed, Inc. Mixture of lafesih magnetic nanoparticles with different curie temperatures for improved inductive heating efficiency for hyperthermia therapy
CN108289856A (zh) * 2015-10-07 2018-07-17 波士顿科学国际有限公司 用以提高热疗的感应加热效率的具有不同居里温度的LaFeSiH磁性纳米粒子混合物
US10661092B2 (en) 2015-10-07 2020-05-26 Boston Scientific Scimed, Inc. Mixture of lafesih magnetic nanoparticles with different curie temperatures for improved inductive heating efficiency for hyperthermia therapy

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