Fe-P
The Fe-P (Iron-Phosphorus) System
Equilibrium Diagram
The assessed Fe-P phase diagram (Fig. 1) is accepted
primarily from [82Kub], which well represents variously
reportedphaseboundarydata The phasesin Fig. 1 are: (1)
the liquid, L; (2) the fcc terminal solid solution, (yFe); (3)
the bcc terminal solid solution, (aFe); (4) Ni3P-type,
tetragonal Fe3P; (5) hexagonal Fe2P; (6) orthorhombic
FeP; (7) FeS2-type orthorhombic FeP2; (8) monoclinic
FeP4; and (9) the terminal phase, (P). The P-rich side of the
phase diagram is unknown. Special points in Fig. 1 are
given in Table 1.
(yFe) Termlnal Solid Solution
The 5Fe ~ y F e and yFe ~ a F e transformation tempera-
tures are 1394 and 912 ~ respectively [82Swa]. The oc-
currence of a ? loop was indicated initially by the presence
and absence, respectively,of djl~tometric anomMies in
0.54 and 0.75 at.% P [25Ess].The homogeneity range of
(yFe)was measured by [27Hau] (thermal analysis,metal-
lography), [29Vog] (metallography),[51Roq] (metallog-
raphy), [62Lor] (magnetic measurements), and [66Fis]
(magnetic measurements) (Fig. 2). The assessed maxi-
m u m solubilityof P in (yFe) is 0.56 at.% at - 1150 ~
[62Lor] (see"Thermodynamics").
(a, Fe) Terminal Solid Solution
The melting point of 5Fe is 1538 ~ [82Swa]. (SFe) and
(aFe) form a continuous phase field surrounding (yFe).
The liquidus and solidus of (aFe) were measured by
[08Ger], [08Sak], [10Kon], [27Han], [27Haul, [29Vog],
[63Wac], and [81Sch]. Some early data [08Ger, 08Sak,
10Kon, 29Vog] are not shown in Fig. 1, becatme the
temperatures were apparently too low, probably due to su-
percooimg.
The solid solubility of P in (aFe) decreases as the tempera-
ture is lowered [00Ste, 08Ger, 15Ste, 18Hau, 18Ste,
Table I Speclal Polnts ofthe Assessed Fe-P Phase Diagram
Composition of the
respective phases,
Reaction
L ~-~SFe ~ ..................... ~176176176176
5Fe ,~ yFe....................................
~Fe ,~ aFe ....................................
L ,~(aFe) + FesP ........................ 17
L + Fe2P ,~Fe3P ........................ 24
L ,~ Fe2P .....................................
L ~ Fe2P + FeP ......................... 40
g ~ L (white P) ...........................
L ,~P (white) .............................
404 Bulletin of Alloy Phase Diagrams Vol. 11 No. 4 1990
ByH. Okamoto
ASM International
31K~, 31Vog]. Quantitative values were obtained by
means of metallography [27Han, 27Hau, 29Vog, 65Kan],
precipitation hardening [24Yen], X-ray analysis [28Kre,
29Obe], lattice parameter measurements [58Sve],
electron probe analyss [70Doa], microprobe and micro-
hardness tests [70Hof], and an X-ray microanalyzer
method [79Ko]. These data are in reasonable agreement,
except for the room-temperature values given by [27Han]
(2.5 at.% P) andby [26Kre] and [29Obe] (3 at.% P). The as-
sessed (aFe) solvns is based on the thermodynamic model
derived by [79Ko] (see "Thermodynamics"). The maxi-
m u m solubilityofP in (aFe) is about 5 at.% at the L ~(aFe)
+ Fe3P eutectictemperature.The equilibriumsolubilityof
P in (aFe) at room temperature isessentiallyzero.
The L ~(aFe) + Fe3P eutectictemperature was reported
a s - 980 [08Ger], 1005 [08Sak], 1020 [10Kon], 1050
[27Haul, 1048 [63Wac], 1040 • 10 [70Doa], and 1039 ~
[81Sch]. The eutectic composition was observed by
[08Sak] at 10 wt.% P (16.7at.% P). Subsequently,similar
values (- 17 at.% P) were observed by [10Kon], [27Hau],
[29Vog], [63Wac], and [81Sch] (except for 22.5 at.% P,
reportedby [70Doa]). The assessedeutecticpoint(17 at.%
P,1048 ~ isa graphicalaverage of thesereports(Fig.1).
Fe3P
The existence of Fe3P was reported by [00Ste] and
[09Lec]. [08Sak] consideredthe melting to be congruent
type at 1104 ~ However, subsequent investigations
showed peritectic melting at -1155 [10Kon], 1166
[27Haul, 1135 [29Vog],or 1173 ~ [81Sch]. The assessed
temperature is 1166 ~ from [27Hau], which isa median
value of the above and isbased on severalthermal arrest
data points (Fig.1).
Fe2P
The existence of Fe2P was reported by [00Ste] and
[09Lec]. The melting temperature was determined to be
Temperature,
at.% P "C Reaction type
0 1538 Meltingpoint
0 1394 Allotropic
0 912 Allotropic
5 33.3 1048 Eutectic
33.3 25 1166 Peritectic
33.3 1370 Congruent
34 1262 Eutectic
100 277 Boilingpoint
100 44.14 Meltingpoint
 Fe-P
1270 [08Sak], 1350 [10Kon], or 1370 ~ [27Hau]. The P- variant points associated with Fe2P (Fig. 1) are accepted
rich limit of Fe2P varies from the stoichiometric value at from the most thorough data, given by [27Haul.
low temperature to 34.0 at.% Pat 1100 "C, according to X-
ray powder diffraction studies [73Car]. The L ~Fe2P + FeP
FeP eutectic temperature is 1262 [27Hart] or 1265 ~ The existence of FeP,which was reported in earlier studies,
[81Sch], and the eutectic composition is 40 at.% P was conf'n-med by [09Lec]. (See "Thermodynamics" for
[27Hau], The composition and temperature of the in- the decomposition reactions.)

Fig. 1 Assessed Fe-P Phase Diagram

Weight Percent Phosphorus
o Io z0 30 40 5o 6o vo 8o 90 ~oo

1538~C " k

,40O
13fl4~
i ~ X L
~ 2 o c

II
ii
ii
ii
ii
+1

~,l ~'11 IjI

II

:l t.........++- ...................
" ~
II
II
II
II
II
II
II
II
II
II
II
II
i
0 10 20 30 40 50 60 70 80 90 100

F'e Atomic Percent Phosphorus p

Atomic Percent Phosphorus

0 IO 20 30 40 50 60 70 80 90 I00

t370~

1166"C
CD

c~
L,

E09
II
II
+I
IPll wl
~., l.w I T,v. i i
ii I
II I
It
....... II
II I
II I
II I
II I
II
II
1
I
II
I I I
I I
~ i ..... ~ T ~'~ ..... i '~+
0 10 20 30 40 50 60 70 80 90 I00
Fe Weight Percent Phosphorus p
Detailof y loopshown in Fig.2. H. Okamoto, 1990.

BulletinofAlloy Phase Diagrams Vol. ii No. 4 1990 405