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Compa a i e s udy o s uc u al and magne ic p ope ies o ibbon and
bulk Ni
55
Fe
19
Ga
26
Heusle alloy
A.F. Manchón-Go dón
a
, J.J. Ipus
a
, M. Kowalczyk
b
, J.S. Blázquez
a,⁎
, C.F. Conde
a
, P. Š ec
c
,
T. Kulik
b
, A. Conde
a
a
Dp o. Física de la Ma e ia Condensada, ICMSE-CSIC, Uni e sidad de Se illa, P.O. Box 1065, 41080 Se illa, Spain
b
Facul y o Ma e ials Science and Enginee ing, Wa saw Uni e si y o Technology, 141 Wołoska s ., 02-507 Wa saw, Poland
c
Ins i u e o Physics, Slo ak Academy o Sciences, Dúb a ská ces a 9, 845 11 B a isla a 45, Slo ak Republic
a icle in o
A icle his o y:
Recei ed 15 June 2021
Recei ed in e ised o m 5 Augus 2021
Accep ed 30 Augus 2021
A ailable online 1 Sep embe 2021
Keywo ds:
Magne ic shape memo y alloys
Ma ensi e s uc u e
Magne os uc u al ansi ion
Heusle alloy
Mel -spinning
abs ac
The in luence o he ab ica ion me hod on he magne os uc u al p ope ies o a Ni
55
Fe
19
Ga
26
Heusle
alloy, ob ained bo h as a ibbon, by mel -spinning, and as a pelle , by a c-mel ing, has been analyzed. I has
been ound ha , while he a c-mel ing echnique leads o he p ecipi a ion o he gamma phase and o a
non-modula ed ma ensi e s uc u e, he alloy p epa ed by mel -spinning p esen s a ully 14M modula ed
ma ensi ic s uc u e a oom empe a u e. The e agonal non-modula ed ma ensi e in he a c-mel ed
bulk sample ans o ms in o he 14M s uc u e a e a long he mal ea men (a 1073 K o 24 h) and
subsequen quenching. Cha ac e is ic empe a u es o he ma ensi ic ans o ma ion a e highe o mel -
spun ibbons han o bulk sample, due o he p ecipi a ion o he gamma phase and consequen di e en
ma ensi e composi ion. Howe e , while he ma ensi ic ans o ma ion empe a u e is p ac ically cons an
in he case o he bulk sample, i changes by
~
150 K in he case o he ibbon sample submi ed o he same
he mal ea men applied o bulk samples. Finally, i was ound ha he ma ensi ic ans o ma ion occu s
in he pa amagne ic egime o bo h ypes o samples.
© 2021 The Au ho (s). Published by Else ie B.V.
CC_BY_NC_ND_4.0
1. In oduc ion
Since he pionee wo k o Ullakko e al. [1], in e es in esea ch
and de elopmen o Ni-Mn-Ga magne ic shape memo y alloys is
inc easing [2–5]. Howe e , he Ni-Fe-Ga sys em has also a ac ed
g ea a en ion due o i s be e duc ili y, a ibu ed o he p e-
cipi a ion o he seconda y phase [6], which could inhibi he win
bounda y mo ion and limi he shape memo y p ope ies o he
sys em. These alloys show ema kable p ope ies, such as ecen ly
epo ed elas ocalo ic e ec s [7–9].
S udies on Ni-Fe-Ga alloys ha e so a mos ly ocused on bulk
polyc ys alline ma e ials p oduced by a c-mel ing and submi ed o
high empe a u e hea ea men s o composi ional homogeniza-
ion [10–14]. Howe e , his p ocess esul s in a ious p oblems, such
as decomposi ion o p ecipi a ion o o he unexpec ed phases,
which nega i ely a ec he unc ional p ope ies o he alloy. Rapid
quenching p epa a ion echniques, like mel -spinning, a e an e ec-
i e single s ep p ocess o p oduce ex u ed polyc ys alline ibbons
wi hou he p ecipi a ion o he seconda y phase [15,16]. Mo e-
o e , i makes possible o sho en (o e en o a oid) long annealing
ea men s, which lead o a educ ion o he ab ica ion ime
and cos .
To ou knowledge, li le da a exis conce ning he e ec o he
ab ica ion p ocess on s uc u e, magne os uc u al beha io and
empe a u es o ma ensi ic ans o ma ion, MT, in Ni-Fe-Ga based
alloys, al hough his kind o s udies can be ound in Ni-Mn-Sn based
Heusle compounds [17,18]. I is also possible o ind compa a i es
s udies o bulk and powde samples in Ni-Fe-Ga alloys [19]. Mo e-
o e , i has been s udied he e ec o he quenching a e on he
magne ic and ma ensi e p ope ies o Ni-Fe-Ga mel -spun ibbons
[16,20] and, ecen ly, he e ec o he exis ence o acancies in
polyc ys alline Ni-Fe-Ga sys ems [21]. Pa icula ly, in Ni
55
Fe
19
Ga
26
composi ion, MT is obse ed sligh ly abo e oom empe a u e [22].
The p esen s udy is de o ed o analyze he in luence o he ab i-
ca ion p ocess on s uc u e and magne os uc u al beha io and on
he empe a u e o MT in a Ni
55
Fe
19
Ga
26
Heusle alloy ob ained bo h
in ibbon shape by mel -spinning and as-pelle by a c-mel ing.
h ps://doi.o g/10.1016/j.jallcom.2021.161819
0925-8388/© 2021 The Au ho (s). Published by Else ie B.V.
CC_BY_NC_ND_4.0
]]]]
]]]]]]
⁎
Co esponding au ho .
E-mail add ess: [email p o ec ed] (J.S. Blázquez).
Jou nal o Alloys and Compounds 889 (2021) 161819
2. Expe imen al
The alloy wi h nominal composi ion Ni
55
Fe
19
Ga
26
was p epa ed
in an induc ion u nace using high-pu i y elemen s (> 99.9%). The
ingo s we e mel ed se e al imes in o de o ensu e homogenei y.
Then, abou 30 g o he ingo was induc ion mel ed in a qua z ube
unde A a mosphe e and ejec ed on o a o a ing wheel wi h a
su ace eloci y o ~ 25 m/s. The hickness and wid h o he ibbon
a e abou 30 µm and 3 mm, espec i ely. Mic os uc u al cha ac e -
iza ion and s abili y o Ni
55
Fe
19
Ga
26
mel spun Heusle alloy can be
ound elsewhe e [23]. A polyc ys alline Ni
55
Fe
19
Ga
26
alloy was also
p epa ed om 5 g o a mix u e o high-pu i y cons i uen elemen s
(> 99.9%) ha we e mel ed ou imes unde A a mosphe e in an a c
u nace. Pa s o he ingo we e cu and annealed a 1073 K o 24 h
in a qua z ampoule illed wi h A and hen immedia ely quenched
in wa e . This sample will be called TTB (The mally T ea ed Bulk). Fo
compa ison, he same he mal ea men was pe o med o he
ibbon, TTR (The mally T ea ed Ribbon).
The chemical composi ion o he samples was analyzed by X- ay
luo escence (XRF) using an EAGLE III ins umen wi h an an ic-
a hode o Rh. The ma ensi ic ans o ma ion s a empe a u e,
Ms a
, as well as he aus eni e ans o ma ion s a empe a u e,
As a
, we e de e mined by di e en ial scanning calo ime y (DSC)
using a Pe king-Elme DSC 7 unde A low and equipped wi h a
cooling sys em (hea ing/cooling a e o
±
20 K/min). The hea ing a e
was chosen in o de o op imize he signal-noise a io o he DSC
measu emen s. Measu ed empe a u es we e co ec ed using he
mel ing empe a u es o an In s anda d (429.75 K).
The mic os uc u al cha ac e iza ion was ca ied ou by X- ay
di ac ion (XRD) and scanning elec on mic oscopy (SEM). XRD
measu emen s we e pe o med in a B uke D8 I di ac ome e (Cu-
Kα, λ = 1.5406 Å). SEM obse a ions we e de eloped in a FEI Teneo
mic oscope ope a ing a 20 kV.
Magne iza ion measu emen s we e pe o med in a ib a ing
sample magne ome e (s anda d op ion o a Quan um Design
Physical P ope ies Measu emen Sys em, PPMS) applying di e en
magne ic ields and a hea ing/cooling a e o
±
1 K/min.
3. Resul s
3.1. Ribbon sample
The s udied Ni
55
F
19
Ga
26
Heusle as-spun ibbon p oduced by
mel spinning shows a ypical columna s uc u e in he ac u e
c oss sec ion (Fig. 1). This consis s o g ains c ys allizing in con ac
wi h he wheel, ollowed by an o de ed columna mic os uc u e
pe pendicula o he ibbon su ace. This is a sign o he quick
c ys alliza ion and as g ow h kine ics o he sample. Pe pendicu-
la ly o he ibbon su ace, he size o he obse ed g ains is as la ge
as he ibbon hickness and hei size in he ibbon plane is
abou 2 µm.
Chemical composi ion o he ibbon has been e alua ed by XRF
echnique, while elec on alence concen a ion pe a om,
e a/
, was
calcula ed om he sum o ex e nal
d
and
s
elec ons o Ni (10) and
Fe (8), and
s
and
p
o Ga (3). The expe imen ally e alua ed chemical
composi ion oge he wi h he
e a/
a e summa ized in Table 1. The e
a e no signi ican di e ences be ween bo h sides o he ibbon and
he composi ion ag ees wi h he nominal one. Addi ionally, poin
analyses and elemen al mappings show a homogeneous dis ibu ion
o he elemen s (no shown).
Fig. 2 shows he oom empe a u e XRD pa e ns aken om bo h
he wheel and he ee su aces o he as-spun ibbon, exhibi ing a
ma ensi e s uc u e. Small di e ences in he in ensi ies o peaks
be ween bo h sides o he ibbon can be obse ed, due o he highly
ex u ed polyc ys alline cha ac e o he ibbons. The spli ing o he
{220} e lec ion o he aus eni e phase in o double s o iple s is
usually aken as an e idence o a e agonally dis o ed ma ensi e
phase, assigned by Wang e al. [24] as space g oup
I mmm4/
. How-
e e , Righi e al. [25] p oposed an o ho hombic
Pnnm
space g oup
wi h a se en-laye ed modula ion on he basis o a Rie eld analysis
o he low- empe a u e XRD da a. On he o he hand, Singh e al.
[26] and K enke e al. [27] iden i ied he monoclinic space g oup
P m2/
o modula ed ma ensi e s uc u es. In o de o e alua e he
space g oup and modula ed s uc u e o he ma ensi e phase, a Le
Bail i ing was pe o med using he di e en space g oups ci ed
abo e. All peaks could only be indexed by he monoclinic
P m2/
space g oup and he ob ained la ice pa ame e s we e
a
= 4.3138(2) ,
b
= 30.2511(17) ,
c
= 5.6190(3) , = 89.028(5)°
(GOF = 1.4). I should be no ed ha
b~
7
a
indica es a se en old in-
c ease in he uni cell leng h along
b
axis, which is in ag eemen wi h
ansmission elec on mic oscopy obse a ions, showing six ex a
spo s be ween wo undamen al maxima, epo ed in ou p e ious
wo k [23]. This ela ion has been ela ed o modula ion o he a omic
posi ions in Ni-Mn-Ga sys ems om bo h neu on [28] and X- ay
di ac ion s udies [29].
DSC scans a 20 K/min we e pe o med o analyze he MT o he
ibbon. The DSC cu e egis e ed du ing a cooling and hea ing cycle
is shown in Fig. 3a along wi h he eco d o he p e ious hea ing up
o 473 K (we conside ed he cycle his way as we do no expec any
i e e sible ans o ma ion o empe a u es below he s a ing
empe a u e o he cycle). The exo he mic and endo he mic peaks
co espond o he o wa d and e e se MT, espec i ely. The onse o
he ma ensi ic ans o ma ion (ma ensi e s a empe a u e,
Ms a
)
du ing cooling and o he e e se ma ensi ic ans o ma ions
(aus eni e s a empe a u e,
As a
) was es ima ed by he wo- an-
gen me hod. The calo ime ic scans e eal ha he mal ea men s
induce a dec ease o he MT empe a u e as he maximum hea ing
empe a u e inc eases, which will be discussed la e .
Fig. 3b shows he empe a u e dependence o magne iza ion
measu ed a hea ing/cooling a es o 1 K/min unde wo di e en
Fig. 1. SEM mic og aph in seconda y elec ons mode o a c oss sec ion o he mel -
spun ibbon.
Table 1
A e age alue o chemical composi ion (a %) and
e a/
o bo h sides o mel -spun
ibbon and he bulk sample om XRF.
Sample Ni Fe Ga e/a
Nominal 55 19 26 7.8
Ribbon ( ee side) 54.72
±
0.12 19.20
±
0.16 26.08
±
0.21 7.79
±
0.03
Ribbon
(wheel side)
54.41
±
0.11 19.22
±
0.15 26.37
±
0.20 7.77
±
0.03
Bulk 54.64
±
0.14 19.39
±
0.11 25.95
±
0.16 7.79
±
0.03
A.F. Manchón-Go dón, J.J. Ipus, M. Kowalczyk e al. Jou nal o Alloys and Compounds 889 (2021) 161819
2
magne ic ields. Upon cooling, only a Cu ie ansi ion has been ob-
se ed in he
M T( )
cu es. Taking in o accoun he XRD esul s, his
ansi ion should co espond o he magne ic ans o ma ion o he
14M modula ed s uc u e (
TC
M14
= 319 K). This esul suppo s hose
ob ained by DSC, showing he MT a empe a u es close o he limi
o measu emen ange o PPMS.
3.2. Bulk sample
A bulk alloy was ob ained by a c-mel ing. The a e age chemical
composi ion o he as-p epa ed sample ob ained by XRF is shown in
Table 1. Fig. 4 ep esen s XRD pa e ns o he as-p epa ed bulk
sample (ASB) and a e annealing a 1073 K o 24 h and hen, im-
media ely, quenched in wa e (The mally T ea ed Bulk sample, TTB).
All he peaks in ASB sample can be indexed wi h a non-modula ed
e agonal L1
0
s uc u e (space g oup
I mmm4/
) and he phase
(space g oup
Pm m3 )
, con i ming he limi a ion o a c-mel ing
echnique o p oduce single-phase samples. A e he he mal
ea men , he 14M modula ed s uc u e (also ound in he as-
mel ed ibbon) is de eloped. In ac , he Le Bail i o he pa e n
e eals he coexis ence o wo phases, he monoclinic s uc u e
co esponding o a ma ensi e phase (
a
= 4.32987(16) ,
b
= 30.3519(6) , y
c
= 5.5537(4) ) and a cubic s uc u e co e-
sponding o he phase (
a
= 3.59974(9)). Again, he ela ion
b
7
a
indica es ha he ype o modula ion is 14M.
Fig. 5 shows ep esen a i e SEM images ob ained o ASB (le
side) and TTB ( igh side) samples. The images ob ained using sec-
onda y elec ons (Fig. 5a and d) show a ypical ma ensi ic mo -
phology, wi h a ian s o winned ma ensi e in he case o he TTB
sample. The small black do s a e po es c ea ed du ing ab ica ion
p ocess. In he case o he backsca e ed images, i can be clea ly
obse ed ha c ys als a e dispe sed inside he ma ensi e g ains,
which con ibu ion was p e iously de ec ed by XRD. These c ys als
a e mo e clea ly obse ed in he case o he TTB sample due o he Fe
en ichmen o he gamma phase wi h he he mal ea men (see
Fig. 5c and ). Table 2 shows he chemical composi ion ob ained by
EDS o he phases ha exhibi he bulk samples. In spi e o he
semiquan i a i e cha ac e o his echnique, i is e iden he Fe
en ichmen and Ga dec ease o he gamma phase in he TTB sample
wi h espec o he ASB one.
The cha ac e is ic empe a u es o MT we e s udied by DSC
(Fig. 6a and b). I can be obse ed la ge exo he mic and endo he mic
peaks upon cooling and hea ing associa ed wi h ma ensi ic and
e e se ma ensi ic ans o ma ion, espec i ely. The ASB sample
exhibi s a b oad MT peak a ound 340 K (on hea ing). The mal
ea men ge s mo e p onounced MT, which sligh ly dec eased o
lowe empe a u es a ound 330 K.
The empe a u e dependences o magne iza ion o he bulk
samples measu ed a wo di e en magne ic ields a e shown in
Fig. 6c and d. The he momagne ic cu es e eal a e omagne ic
beha io wi h a Cu ie empe a u e a 285 and 278 K, o ASB and
TTB, espec i ely. Following he XRD esul s, hese Cu ie ansi ions
Fig. 2. a) XRD pa e ns o Ni
55
Fe
19
Ga
26
as-spun ibbon o he wheel, WS, (uppe ) and he ee, FS, (bo om) sides, espec i ely. b) Le Bail i ing o XRD pa e n o he as-spun
ibbon (FS) wi h
P m2/
space g oup. The open ci cles and he solid con inuous lines ep esen obse ed and calcula ed pa e ns, espec i ely. The di e ence plo is shown a he
bo om. The inse depic s a ho izon ally zoomed plo in a limi ed ange o 2 . The B agg peaks a e labeled acco ding o he no a ion o he monoclinic sys em usually used o
desc ibe he modula ed 14M s uc u e.
Fig. 3. a) DSC scans o ibbon samples measu ed a 20 K/min in he icini y o he
ma ensi ic ans o ma ion du ing hea ing and cooling cycles. A ows indica e hea ing
and cooling pa hways. b) The momagne ic measu emen s on as-p epa ed ibbon
upon cooling (blue) and hea ing ( ed) om 400 o 100 K and unde di e en ex e nal
applied magne ic ields. Inse shows hei co esponding
dM dT/
cu es.
A.F. Manchón-Go dón, J.J. Ipus, M. Kowalczyk e al. Jou nal o Alloys and Compounds 889 (2021) 161819
3
should co espond o he ma ensi e phase. The e o e, upon cooling,
ans o ma ion sequence is pa amagne ic aus eni e pa amagne ic
ma ensi e e omagne ic ma ensi e. The MT empe a u es a e in
good ag eemen wi h hose obse ed by DSC. The p esence o he
gamma phase is esponsible o a non-ze o magne iza ion
abo e
As a
.
4. Discussion
The in luence o he p oduc ion me hod on magne o-s uc u al
beha io has been sys ema ically in es iga ed. In o de o e alua e
he s abili y o MT in he s udied samples, di e en he mal cycles
we e done up o a highe maximum empe a u e each ime. Fig. 7
shows, as a unc ion o he uppe limi empe a u e eached in each
cycle, he e olu ion o he pa ame e s o he MT (
Ms a
and
As a
, and
he a e age ans o ma ion hea in he o wa d and e e se ans-
o ma ion). Fo he ibbon sample i can be obse ed ha he em-
pe a u e a which he MT occu s con inuously dec eases wi h
Fig. 4. a) XRD pa e ns o Ni
55
Fe
19
Ga
26
as-p epa ed bulk. b) XRD pa e n o he TTB sample (open ci cles) and i s Le Bail i ing using
P m2/
and
Pm m3
space g oups ( ed line). The
di e ence (black line) is shown a he bo om. The inse depic s a ho izon ally zoomed plo in a limi ed ange o 2 .
Fig. 5. SEM mic og aphs ob ained using seconda y (a and d) and backsca e ed elec ons (b and e) and co esponding composi ional maps ob ained by EDS (c and ). a–c
co espond o ASB sample and d– o TTB sample. The ho izon al ba co esponds o 50 µm. Ni, Fe and Ga elemen s a e ep esen ed in g een, blue and magen a, espec i ely.
Table 2
Chemical composi ion (a %) and
e a/
o he bulk samples ob ained by EDS.
Ma ensi e phase Gamma phase
Sample Ni Fe Ga e/a Ni Fe Ga
ASB 55(2) 19(2) 26(3) 7.80 56(2) 24(2) 20(3)
TTB 56(2) 18(2) 26(3) 7.82 56(2) 28(2) 16(3)
A.F. Manchón-Go dón, J.J. Ipus, M. Kowalczyk e al. Jou nal o Alloys and Compounds 889 (2021) 161819
4
inc easing he uppe limi empe a u e. The he mal hys e esis, de-
ined as
As a
-
M,
s a
is p ac ically cons an un il he en halpy o
ans o ma ion d ops signi ican ly ( o empe a u es highe han
773 K), which could be associa ed o he p ecipi a ion o he gamma
phase. These esul s a e in ag eemen wi h hose collec ed by Tolea
e al. [30], whe e i is shown ha he hea ea men s abo e MT
p omo e a shi o lowe empe a u es in ibbons o Ni-Fe-Ga-Co
composi ion. In any case, he esul s ob ained sugges ha he
ibbon unde goes a s uc u al modi ica ion du ing he hea ea -
men s pe o med. In he case o ea men s a low empe a u es
(< 573 K), elaxa ion o s esses s o ed du ing ab ica ion o he
ibbons occu s. T ea men s a high empe a u es (> 773 K) induce
p ecipi a ion and g ow h o he gamma phase [23].
Unlike he esul s ob ained o he ibbon, he pa ame e s asso-
cia ed o MT emain p ac ically cons an in he case o he bulk
samples, a leas o he ange o empe a u es analyzed. As i was
p e iously shown (see Fig. 6a and b), MT occu s a sligh ly highe
empe a u es o he ASB sample han o he TTB one. This dis-
placemen could be associa ed wi h he Fe en ichmen o he gamma
phase in he case o he TTB sample. Mo eo e , bo h ans o ma ion
en halpy and empe a u e a which he ansi ion occu s a e lowe
o he bulk sample han o he ibbon sample, due o he exis ence
o he gamma phase. This phase, on he one hand, limi s he ac ion
o ans o mable phase, educing he ans o ma ion en halpy and,
on he o he hand, modi ies he elec onic alence concen a ion pe
a om o he ma ensi e phase, wi h which MT exhibi s a s ong de-
pendence [31]. The e o e, en halpy change could be used o es ima e
he ac ion o he gamma phase in he TTB sample i a 100% o he
14M s uc u e is assumed o he as-spun ibbon. The esul s o his
analysis lead o an app oxima ely 20% o he gamma phase in he
TTB and ASB samples. Assuming he composi ion o he alloy shown
in Table 1 (Ni
54.64
Fe
19.39
Ga
25.95
) and he composi ion o he gamma
phase shown in Table 2 (Ni
56
Fe
24
Ga
20
o ASB and Ni
56
Fe
28
Ga
16
o
TTB), we can oughly es ima e he composi ion o bo h phases and
om hem he
e a/
alues, esul ing 7.72 and 7.67 o he ASB and TTB
samples, espec i ely. The e o s o his es ima ion as well as he
e a/
alues p esen ed in Table 2 a e abo e 10%, and hus he quan i a i e
alues mus be aken wi h cau ion. Howe e , quali a i ely, he en-
ichmen in Fe and impo e ishmen in Ga o he gamma phase mus
indi ec ly imply a dec ease in he
e a/
alue o he ma ensi e phase,
which is poin ed by he EDS esul s in Table 2.
In o de o show he s uc u al modi ica ion o he ibbon and o
analyze he dec ease o he en halpy in he successi e he mal cy-
cles, di e en pieces o ibbon we e hea ed a 10 K/min up o di -
e en empe a u es and hen annealed o 10 min. I should be
men ioned ha he annealing empe a u es, al hough abo e he
ma ensi ic ansi ion empe a u e o he as-spun ibbon, a e below
he o de -diso de phase ansi ion L2
1
-B2 empe a u e
(
~
973 K) [32].
Fig. 8 shows XRD pa e ns o he annealed ibbons along wi h
ha o he as-spun ibbon. As i was p e iously indica ed, he
s uc u e o he as-spun ibbon co esponds o a 14M modula ed
phase. The annealings a 673 and 773 K only p oduce a small a -
ia ion o he la ice pa ame e s, which modi ies he
b a/
a io. In ac ,
Fig. 6. a) DSC cu es measu ed a 20 K/min in he icini y o he MT du ing con inuous hea ing and cooling cycles o a) as-p epa ed, ASB, and b) he mally ea ed, TTB, bulk
samples. A ows indica e hea ing and cooling pa hways. The momagne ic measu emen s upon cooling and hea ing om 400 o 100 K unde di e en ex e nal magne ic ields o
c) ASB and d) TTB samples. Uppe inse s in c) and d) show he co esponding
dM dT/
cu es a 0.01 T. Middle inse s in c) and d) depic a zoomed plo in a limi ed ange o
empe a u es.
A.F. Manchón-Go dón, J.J. Ipus, M. Kowalczyk e al. Jou nal o Alloys and Compounds 889 (2021) 161819
5

when he same ype o Le Bail i ing (no shown) is applied o hese
pa e ns,
b a/
= 6.68 and 6.67 o he samples annealed a 673 and
773 K, espec i ely, being 7.01 o he as-spun ibbon.
The a ia ion o he la ice pa ame e s is ela ed o he p e-
cipi a ion o he phase, which modi ies he composi ion o he
modula ed s uc u e and limi s he p opo ion o main phase ha
can ans o m and, he e o e, dec eases he ansi ion en halpy ob-
ained by DSC. A e annealing a 873 K, he monophasic cha ac e o
he ibbon clea ly disappea s, and he ma ensi ic modula ed
s uc u e gi es ise o wo phases, he aus eni e and phases, al-
hough small aces o he modula ed phase can s ill be obse ed
(see maximum a
~
2 = 46º). The e o e, he MT shi owa ds lowe
empe a u es can be unde s ood as a p og essi e des abiliza ion o
he 14M modula ed phase due o he p ecipi a ion o he gamma
phase, leading o a s abiliza ion o he aus eni e phase a oom
empe a u e (RT).
In o de o comple ely s abilize he aus eni e phase a RT, pieces
o ibbon we e annealed a 1073 K o 24 h in a qua z ampoule illed
wi h A and hen immedia ely quenched in wa e sample (same
ea men pe o med o he bulk sample), ha will be called TTR
(The mally T ea ed Ribbon). The co esponding XRD pa e n o his
sample (Fig. 8) exhibi s a mix u e o wo phases ha can be indexed
as L2
1
aus eni e and phases. Fig. 9 shows he empe a u e de-
pendence o magne iza ion o sample. Upon cooling, he ans o -
ma ion sequence is pa amagne ic aus eni e e omagne ic
aus eni e e omagne ic ma ensi e. I means ha he e omag-
ne ic-pa amagne ic ans o ma ion is inished (o nea ly inished)
be o e he ma ensi e s a s o o m (see inse Fig. 9). The e o e, he
obse ed Cu ie empe a u e co esponds o he aus eni e phase,
TC
A
= 285 K, which is lowe han
TC
M14
. On he o he hand,
As a
= 265 K
and
Ms a
= 250 K.
Table 3 shows he MT empe a u es,
TM
, and he Cu ie em-
pe a u es o he ma ensi e,
TC
M
, and he aus eni e,
TC
A
, phases o he
di e en s udied samples ob ained by magne ome y measu e-
men s. MT beha io is signi ican ly di e en be ween hem. While
TM
is p ac ically cons an in he case o he bulk, his pa ame e
changes by
~
150 K in he ibbons. This signi ican a ia ion can be
ela ed o he g ain e inemen , in e nal s esses and high densi y o
Fig. 7. a) Tempe a u es co esponding o he ma ensi ic ans o ma ion s a ,
Ms a
,
du ing cooling and e e se ma ensi ic s a empe a u e,
As a
, and b) a e age hea o
ans o ma ion as a unc ion o he uppe limi empe a u e a ained in each cycle.
Filled symbols a e used o ibbon samples and emp y symbols a e used o as-p e-
pa ed ( ed) and he mally ea ed (black) bulk samples.
Fig. 8. XRD pa e ns o Ni
55
Fe
19
Ga
26
ibbons annealed 10 min a he ma ked em-
pe a u es along wi h he pa e n o he ibbon submi ed o he same long he mal
ea men o he bulk sample.
Fig. 9. The momagne ic measu emen s upon cooling and hea ing be ween 400 and
100 K on he mally ea ed ibbon sample a 1073 K o 24 h unde di e en ex e nal
magne ic ields. Inse shows he co esponding
dM dT/
cu es a 0.01 T.
Table 3
Cha ac e is ic ans o ma ion empe a u es (ma ensi ic ans o ma ion
TM
and Cu ie
empe a u es o he ma ensi e,
TC
M
, and he aus eni e
TC
A
, phases), o he as-p epa ed
and he mal ea ed samples (TTR and TTB), ob ained by magne o he mal measu e-
men s. In he case o he
TC
M
he s uc u e o he ma ensi e phase has been indica ed.
ND: No -de ec ed.
Sample
TM
(K)
TC
M
(K)
TC
A
(K)
Ribbon As-p epa ed 400 320 (14M) ND
TTR 257 ND 285
Bulk As-p epa ed 328 283 (L1
0
) ND
TTB 320 278 (14M) ND
A.F. Manchón-Go dón, J.J. Ipus, M. Kowalczyk e al. Jou nal o Alloys and Compounds 889 (2021) 161819
6
la ice de ec s such as disloca ions and acancies in oduced du ing
he mel -spinning p ocess [33], leading o a high dependence o
TM
wi h he he mal ea men s. On he o he hand, al hough i has
been epo ed ha
TM
depends on se e al ac o s, he dominan one
is he chemical composi ion [14,34]. Thus,
e a/
e ec should be aken
in o accoun in he s udied samples due o he p ecipi a ion o he
phase de eloped a e he he mal ea men s.
Al hough he Cu ie empe a u es o he 14M modula ed phase o
he ibbon and he bulk samples di e om each o he , his di e -
ence is smalle , as expec ed, han he di e ences ound o
TM
. In
ac , he dependence o Cu ie empe a u es,
TC
M
and
TC
A
, on
e a/
is less
p onounced han in he case o
TM
[35]. I is also wo h men ioning
he small a ia ion o
TM
( ew deg ees) a e he bulk is he mally
ea ed e en despi e he modi ica ion o he s uc u e o he ma -
ensi e. Finally, he
TC
A
was only de ec ed in he case o he quenched
ibbon, he bulk samples being pa amagne ic in he empe a u e
ange in which aus eni e is de ec ed.
5. Conclusions
Nickel- ich polyc ys alline Ni
55
Fe
19
Ga
26
Heusle alloy was p o-
duced using mel -spinning and con en ional cas ing echniques. The
mic os uc u e and magne os uc u al ans o ma ion beha io ha e
been analyzed. The main conclusions ob ained a e:
•The c ys al s uc u e o sample p epa ed in a ibbon shape ex-
hibi s a single-phase ma ensi e modula ed 14M s uc u e a
oom empe a u e. The a c-mel ing echnique did no allow us o
ob ain a single-phase sample, ob aining a coexis ence o a non-
modula ed ma ensi e s uc u e and gamma phase a oom
empe a u e. Howe e , he modula ed phase in he bulk is de-
eloped a e a long- e m hea ea men ollowed by wa e
quenching. This ea men also p omo es an Fe en ichmen o he
gamma phase.
• Cha ac e is ic empe a u es o he ma ensi ic ans o ma ion a e
lowe o he bulk sample wi h espec o he mel -spun ibbons.
This may be connec ed wi h he change o he
e a/
pa ame e due
o he p ecipi a ion o he gamma phase in he case o he bulk.
•Fo he bulk alloy he pa ame e s o he ans o ma ion (ma -
ensi e empe a u e and en halpy) a e p ac ically cons an in he
ange o empe a u es analyzed he e, whe eas hese pa ame e s
signi ican ly change in he case o he ibbons; bo h dec ease
wi h he inc ease o he annealing empe a u e.
• The ma ensi ic ans o ma ion akes place in he pa amagne ic
egime in he case o he as-spun ibbon and he he mally
ea ed bulk.
CRediT au ho ship con ibu ion s a emen
A.F. Manchón-Go dón: Concep ualiza ion, Expe imen s, Fo mal
analysis, W i ing – o iginal d a . J.J. Ipus: Expe imen , Supe ision,
W i ing – e iew & edi ing. M. Kowalczyk: Expe imen , Supe ision,
W i ing – e iew & edi ing. A. Wójcik: Expe imen , Supe ision,
W i ing – e iew & edi ing. J.S. Blázquez: Concep ualiza ion,
Me hodology, Supe ision, W i ing – o iginal d a , Resou ces. C.F.
Conde: Me hodology, Supe ision, W i ing – e iew & edi ing. W.
Mazia z: Resou ces, W i ing – e iew & edi ing. P. Š ec S .: Samples,
Resou ces, Supe ision, W i ing – e iew & edi ing. T. Kulik:
Resou ces, W i ing – e iew & edi ing. A. Conde: Resou ces,
Me hodology, Supe ision, W i ing – e iew & edi ing.
Decla a ion o Compe ing In e es
The au ho s decla e ha hey ha e no known compe ing i-
nancial in e es s o pe sonal ela ionships ha could ha e appea ed
o in luence he wo k epo ed in his pape .
Acknowledgemen s
This wo k was suppo ed by AEI/FEDER-UE (P ojec s US-1260179
and P18-RT-746) and he PAI o he Regional Go e nmen o
Andalucía. Suppo o p ojec s VEGA [G an no. 2/0144/21] and APVV
[G an no. APVV-19-0369] is acknowledged. A.F. Manchón-Go dón
acknowledges a VPPI-US Fellowship. The magne ic measu emen s
we e pe o med in he ame o he polish Na ional Cen e o
Resea ch and De elopmen unding (G an no.: Techma s a eg2/
410941/4/NCBR/2019).
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