Journal of Crystal Growth 132 (1993) 315-328

North-Holland

Review paper

The Verneuil flame fusion process: substances

M. Ueltzen
Labor fiir Supraleitertechnologie und Kristalltechnik, FB Chemieingenieurwesen, FH Miinster,
Stegenwaldstrasse 39, D-48565 Steinfurt, Germany
and FB Physik, Martin-Luther-Universitiit, D-06108 Halle - Wittenberg, Germany

Received 9 March 1993; manuscript received in final form 29 April 1993

On the occasion of the 100th anniversary of the Verneuil method, a brief review is given on the applications of this process in
the field of crystal growth and materials processing together with a comprehensive bibliography.

1. Introduction showed that it was possible to melt alumina pow-

der completely and to grow synthetic rubies of 12
A hundred years ago Verneuil developed a to 15 ct (2.5 to 3 g) with diameters of 5 to 6 mm
process for the production of synthetic rubies in 2: h [2]. Further work was carried out by
(plis cachet& 4752-23.12.1891, 4849-19.12.1892, Verneuil in the field of coloured alumina crystals,
although this was not published until 1910 [l]). e.g. blue sapphire [5] and alumina-rich solid solu-
The main problem was in supplying sufficient tion spinels [6].
heat to reach the high melting point of alumina at A full review of Verneuil’s life and work in
2050°C. This problem was diminished by melting Paris at the time of his discovery has been given
only a small volume of material in fine grained by Nassau in a series of papers [7-111.
form. The main part of a Verneuil apparatus (see
fig. 1) is a vertical inverted oxyhydrogen burner.
Crystal powder is fed to the inner gas stream, 2. Substances
which is in general oxygen. The flame burns into
a ceramic muffle, where a seed crystal is posi- Until 1945, crystal growth by flame fusion was
tioned in such a manner that only a thin film limited to alumina and nonstoichiometric magne-
melts on the top surface. The molten feed mate- sia alumina spinels, the major applications being
rial drops into the molten layer and if the powder directed towards synthetic gem stones. Research
flow and the crystal retraction rates are well was done in the field of optically activated crys-
balanced, the crystal will grow with the liquid- tals. The contemporary reports of the field infor-
solid phase boundary kept at a constant height in mation agency (FIAT) give insight in production
the flame. and research at that time [12,13]. After 1945, also
Verneuil’s burner [2] consisted of two concen- rutile was grown by flame fusion in America [14]
tric tubes with conical ends. The diameter of the and Europe [15], whilst in the Soviet Union, the
inner tube was 2.2 mm and the diameter of the Verneuil process was optimized by Popov’s devel-
outer tube was reduced from 17 to 14 mm with a opments [16,17] in relation to the quality of the
nozzle length of 47 mm. The nozzles were made crystals obtained. With a new designed burner
of brass or copper; it was not necessary to use muffle system, it was possible to work with more
platinum. The burner worked with lighting-gas or homogeneous flames making the heat exchange
oxyhydrogen [2-41. With such a burner, Verneuil with the crystal powder more effective. This re-

0022.0248/93/$06.00 0 1993 - Elsevier Science Publishers B.V. All rights reserved

 316 M. Ueltzen / Vemeuilframe fusionprocess: substances

Table 1
Crystals grown by flame fusion

Substance Tsr. (“Cl Diam. x length (mm) Remarks Ref. (year)

Single arides

4203 d6 3g [21(1904)
AI,O, : Fe,Ti Blue sapphire PI (1910)
AI2o3 d18 [18] (1934)
d25x63 [121(1945)
d2(4) x 100 [191(1954)
d25 [20](1965)
d15xllO [21](1969)
d28 x 330 [22] (1972)
d2(4) x 55 [23](1972)
d55 x 100
d9Ox 170 E.g. 240 cm2, 500 g [24] (1968)
TiO, rutile [151(1949)
[25] (1950)
[26] (1958)
[27] (1963)
[28] (1968)
[29] (1989)
d15x30 I301 (1949)
d35 [20] (1965)
CT203 d8xSO [311(1955)
d10 [32](1965)
d12x30 [33] (1966)
d15x70 65 g without cracks [341(1975)
NiO-Co0 d8x50 [311(1955)
Coo-MnO
NiO-MnO
Fe304
MnO [351(1959)
NiO d5 [36] (1959)
NiO, MnO d8x60 [371(1959)
MnO d9x25 [38] (1960)
COO, NiO 13910964)
Fe30, [40] (1968)
MnO, Mn,O,
COO d6x18 [41] (1963)
NiO d25 [20] (1965)
NiO [42](1969)
NiO : Li [431(1971)
Coo-NiO 1935-1990 dlOx40 WI (1972)
NiO 1990 dlOx60 Bicrystals [45](1978)
Be0 2530 d5 Bromellite [46](1957)
Be0 : Cr d12 [47] (1973)
sc2o3 2300 d4x45 [48] (1958)
Ga203 1850 d9x25 2x8x20mm3 twin free [49] (1964)
Ta20, 8 g, twins [SO](1965)
Ta2% [51] (1972)
[52] (1981)
CaO : Nd d12 [471(1973)
Y,O, 2410 d9x25 [53](1961)
yb203
Wd-a0.d203
 M. Uelrzen / Verne& flame fiuion process: substances 311

Table 1 (continued)

Substance T,, (“0 Diam. X length (mm) Remarks Ref. (year)

Y,O, : Cr 2410 [54](1961)

y203 2410 d6x25 [55] (1962)
[56] (1962)
SE,03 type C d3x50 [56] (1962)
S&O3 type A 2250 d6x40 [57] (1966)
type B 2350 d5x40
typeC 2450 d4x40
S&O3 type C 2450 d2 [58] (1967)
SE2o3 [59] (1967)
SE,O,-SE,O, Binary mixtures [60] (1968)
[61] (1971)
SE,O, type A 2350 d3(10) x 30 L+O,, Pr,O,, Nd,O, [62] (1974)
Type B 2400 Sm,O3, Eu,O,, Gd203 [63] (1982)
Type C 2480 HO2039 Er203, fi,O, &OS, SC2031
Y,O,-SE,O, 1750 d4 [64] (1976)
Lu,O,-SE203 [65] (1979)
C-C, C-A, C-B types

Spinels (see al.90 ferrires)

MgO-Al,O, : Co Al-rich (100: 11) [61(1908)

MgO-AI,O, Nonstoich. 3.56 or 3.58 [66] (1943)
d25x63 Nonstoich. [121(1945)
d20x50 [67] (1957)
MgAIzO4 d9x13 [68] (1960)
Mg0.(0.8-3.5)Al,03
MA204 d3x50 Cover of sintered material reduces [56] (1962)
temperature gradients
MgO-Al,O, 1925-2135 [69] (1962)
MgAl,O,-Al,O,:Cr [70] (1962)
[27] (1963)
MgAl,O, d6x50 [71] (1965)
Mg0.3A1203 d25 [20] (1965)
MN204 1900-1940 d8x22 [72] (1967)
MgO.(l-6)Al,O, [73] (1968)
MgO.(1.7-2.5)Al,O, d25x40 Substrates [74] (1969)
MgO-Al,O, d20 x 50 [75] (1969)
Mti1204 d20x60 [76] (1972)
MM204 d50 [771(1975)
MnO-Al,O, Nonstoich. Mn-AI spinels [78] (1982)

Tungstates

CaWO, 1576 d4x4 Scheelite [791(1949)

CaWO, 1535 d3x125 [801(1950)
CdWO, 1325 d3x125
CaWO, [26] (1958)
BaWO,
CaWO, d10 x 20 [811(1959)
CdWO,
CaWO, Nonstoich. water containing melt [82] (1966)
CaWO, 25 [83] (1969)
SrWO,
BaWO,
318 M. Ueltzen / Vemeuil pame fusion process: substances

Table 1 (continued)

Substance Ts,. (“C) Diam. x length (mm) Remarks Ref. (year)

Silicates

dlOx20 Mullite [84] (1950)

1790 Mullite [85] (1950)
Solid solution mullite-alumina [861(1951)
2AI,O,.SiO, d7x7 Mullite [87] (1956)
1945 d8x25 Mullite [88] (1958)
BaAl,Si,Os Celsian [861(1951)
CaSiO, Pseudowollastonite
CaSiO, : Zn
MgSiO, Clinoenstatite
Mg,SiO, Forsterite
Mg,SiO, 1898 dl0 x 50 Forsterite [89] (1967)
Ca,SiO, Larnite [901(1975)
Ca,SiO,-Ca&PO,), 2130 Polycrystalline, great single [91] (1971)
crystalline pieces
6Ca,SiO,.Cas(PO& [92] (1981)
Be,Al,Si,O,s:Cr Emerald [93] (1963)

Ferrites

MO-Fe,O, M = Ni, Co, Fe-rich [941(1954)

MFe,O, M = Mn, Mg, Cd, Zn
ferrospinels
d8x50 M = Fe, Ni, Co, Mn [311(1955)
d5x55 M=Mn [95] (1958)
d8x50 M = Mn, Co, Ni, Zn, Ni-Zn, [96] (1958)
Mg-Mn, Mn-Zn
d8x60 M = Mn, Co-Mn, Cu-Mn [371(1959)
d7x25 Ni-, Mg-ferrites [971[1959)
5X4X4 Co-, Mn-ferrites [981(1959)
Fe 3 +4’,04 d8x60 [37] (1959)
NiO.Fe,Os Ni-, Mg-, Mg-Mn-ferrites [99] (1960)
MgO.Fe,O,
Ni,Fe,_,Fe,O, 1400-1800 d4-dl0 [loo] (1961)
Mg,Fet-,FezO,
(MgO)a.ss(MnO)a.,s
.(Fe,OJa.4
MgO-Fe,O, Shell with Fe,O, precipitates [loll (1961)
MnO.Fe,Os Textured Fe,O, [102] (1962)
precipitates
Mg-, Ni-, Mn-ferrites [103] (1964)
Fe’+ Fe 0 1600-1700 d5x35 Ferrospinels [104] (1966)
Rzt(Fe,&;ad4
R’+(Fe,Al),O,
NiO-Fe,O, 1650 d6 Nonstoich. > 1.2 [105] (1968)
Mn,Fes-,04+, 1570-1590 dlOx60 [106] (1969)
(Mn,Cu)Fe,O, Copper evaporation [106] (1969)
MgO-MnO-FeaO, 1800 d6 [107] (1969)
NiO-ZnO-Fe,O,
(Co,Ni)Fe,O, d2-d5 Ball shaped [108] (1980)
Mna.,2Zna.s,Fe2.a404 11 [109] (1985)
BaFet2Ots Ferroxdur, small crystals, [371(1959)
textured: c-axis perpendicular
to growth direction
 M. Ueltzen / Verne& frame fusion process: substances 319

Table 1 (continued)

Substance Tsr. (“Cl Diam. X length (mm) Remarks Ref. (year)

BaFe,,% [llO] (1963)

SrF%% d18x30 c-axis perpendicular to [ill] (1967)
growth direction
polycrystalline shell
BaFe&,
Titanates

SrTiO, 2100 d15 x35 [1121(1955)

dlOx 15 [113] (1962)
d7x30 [114] (1962)
d18 [20] (1965)
d15 x 30 [115] (1976)
1920 d18x50 TiO,-rich bubbles [116] (1977)
d20 [117] (1991)
SrTiO,-LaAlO, d10 [118] (1983)
CaTiO, [119] (1958)
CaTiO, 1960 d12 x 25 Perovskite [120] (1962)
BaTiO, : Sr d10 x 15 [113] (1962)
BaTiO, : Sr 1580 [1211(1974)
MgTiO, : Cr d3xlO [122] (1963)
MgTiO, : Fe,Mn d15 [123] (1979)
Mg,TiO, 1840 Peritectic compound [124] (1956)
1840 d4xlO Peritectic compound [125] (1974)
Y,Ti,O, 1950 dlOx30 [126] (1974)

Aluminates (see also spine& garnets)

NiAl,O, d8 x 20(50) [31](1955)

coAl,o,
MnAl,O,
S+Jdh9 1960 d8xlO Peritectic compound [127] (1981)
SW2019 [128] (1981)
LnMgAW19 1700-2000 d10 x 40 Ln = La, Pr, Nd, Sm, Eu, Gd, La-Nd [129] (1981)
LaMA&& dlOx50 M2+ = Ni, Co, Mn, Mg-Mn [1301(1983)
LaMAW% 1850 d15 x 30 M = Ni, Co, Fe, Mn [1311(1983)
LNMgAW,, 1800 dlOx30 LN = La, Ce, Pr, Nd, Sm, Eu, Gd [132] (1986)
LaMAI,,O,, M = Mn, Co, Fe
LaMgAl,,-,Ti,% 1800 dS(10) x 50 Growth in a direction [133] (1988)
La_,Ce,MgAl,,O,, 1800 dlOx40 Some large crystals, 7 X 7 X 2 mm’, [134] (1988)
growth in a direction
LaMgAl,,% 1950 [1351(1985)
LaAlO, [136] (1990)

Garnets

YFePl2 YIG, peritectic compound, other [137](1959)

phases at higher growth rates
YIG [37] (1959)
Y3Fe,% 1500 dSx25 YIG [138] (1960)
Y,Al,O,, :Yb YAG [139] (1960)
Y3A1,012 d6x38 YAG [71] (1965)

Others

wo4 1810 [140] (1968)

LaNbO, d4xlO Also other LnAO, [141] (1969)
YNbO, compounds tested
320 M. Ueltzen / Verneuil flame fusion process: substances

Another important application is the provision

of materials for high-T, research, such as the
cuprates Y-Ba-Cu-0 [146] and Bi-Sr-Ca-Cu-
0 [146-1481. It is difficult to maintain the proper
stoichiometry of these superconducting com-
pounds; the boules are also multiphased and
polycrystalline. However, by using a laser-
Verneuil technique (La,Sr),CuO, [149] and
YBa,Cu,O,_, [150] boules have been grown, but
only as small sized single crystals of 0.5 X 0.5 X
0.04 mm3 dimensions within multiphased sam-
ples. The main problems are the incongruent
melting of the superconducting compounds, the
strong evaporation of copper oxide in the oxyhy-
drogen flame, and the change of the valence state
of copper [151]. However, the possibility of the
adjustment of very high temperature gradients at
the phase boundary in Verneuil’s geometry offers
the technical possibility of producing textured
Fig. 1. Verneuil apparatus.
superconducting cuprates [152].
During the last 50 years many substances have
been grown as single crystals by the Verneuil
sulted in a higher quality of the grown crystals flame fusion process (see table 1). The process is
[17]. Other work was directed towards technical limited mainly to high melting oxides with melt-
applications for alumina crystals. The growth of ing points in the range of 1500 to 2500°C but
small diameter crystals was introduced in order to some incongruently melting compounds have also
avoid cutting the very hard sapphire. Since 1950, been produced.
other high melting oxides and mixed oxides, e.g.
silicates, tungstates, ferrites and titanates, have
also been grown (cf. table 1).
In the last 10 years the growth of aluminates 3. Powder preparation techniques
(cf. table 1) for use as laser crystals [133,134] or as
substrate materials for magnetic [127] or super- The success of crystal growth by flame fusion
conducting [136] layers has been developed. depends on the constitution of a feed of low bulk
Strontium titanate in particular has become a density with a high degree of purity. The prepara-
standard material of Verneuil crystal growth [142]. tion of a free-running micron-sized powder is a
Work has also been carried out to grow other crucial point in flame fusion technology [1531.
high melting oxides, e.g. NiO [143], V,O, [144], The normal feed material used in the growth of
Ta,O, [52] and TiO, [145,29]. Today, the main sapphire and ruby boules is prepared by calcining
applications for single crystals produced by flame a double salt of aluminium and ammonium sul-
fusion are artificial gem stones, e.g. metal doped phate at temperatures of 1000 to 1100°C (see
alumina, spine& or strontium titanate, laser crys- Verneuil’s patents in 1891 and 1892 [ll> and by
tals like ruby or magnetoplumbite-type alumi- passing the product through a screen (e.g., 170
nates, substrates for superconducting layers, e.g. mesh). The alumina powder thus produced is a
strontium titanate and lanthanum aluminate, and light, fluffy, open-structured mass of low density
crystals for optics as high temperature resistant [20,85]. To eliminate the noxious gases produced
windows, or for bearings as abrasion-resistant by sulphate materials, there is an alternative
materials. method for preparing the feed material using
 M. Ueltzen / Verneuil flame fusion process: substances 321

hydroxides [154], which avoids agglomeration it flows poorly and vaporizes in the flame. p-
problems. Ga,O, was obtained by sintering the powder at
Spray drying offers a further route for making 1250°C. This powder is more stable in the flame
an alumina powder with a secondary particle size and suitable for crystal growth [49].
of 10 to 70 pm, which has good flow properties For the growth of mixed oxides like alumi-
[155]. The concentration of small bubbles in the nates, titanates, or silicates obtaining the correct
crystals, which are typical of Verneuil boules, is ratio of metal atoms in the mixture is an addi-
diminished with such a feed. For other sub- tional problem. Alumina-magnesia spine1 pow-
stances, e.g. spinel, r-utile, titanates or YAG, the ders are prepared by the calcination of alu-
preparation of the feed material in a spherical minium ammonium sulphate (alum) and magne-
granular form leads to an improved yield of single sium ammonium sulphate (pseudoalum) [121 or of
crystals of uniform quality [156]. Spheres of this magnesium sulphate and alum [721 in the re-
kind may be produced by passing the powder quired ratios. Bauer and Gordon [861 published
through the oxyhydrogen flame of a Verneuil methods suitable for the preparation of silicate
apparatus. A mixture of such spheres with un- powders. The simplest method is mixing the ox-
treated powder in suitable proportions can result ides (or carbonates, sulphates, etc.) in the proper
in a free-flowing feed material, enabling a steady proportions to attain the required composition.
metered flow rate of material [157]. A method The calcination can take place at a temperature
using the anodic dissolution of aluminium has several hundred degrees below the fusion point
also been employed to produce alumina powder of the compound. The double salt method is the
more quickly and with an increased dispersibility best one from the viewpoint of purity, homogene-
and flowability compared with that obtained by ity and density. Bauer and Gordon used the re-
other methods [158]. Tseitlin [159-1611 showed spective alums Ry(NH4)2(S04)4 * 24H,O or
that the addition of 1% to 20% aluminium fluo- pseudoalums R2+(NH,),(S0,), .6H,O accord-
ride in the alumina feed acts as a mineralizer, ing to whether trivalent or bivalent cations were
and thus the limits of doping with pigments, e.g. required. During the calcination, the alum melts
Cr, Ti, Fe, Ni, V or Co, are extended and the and results in a homogeneous mixture with the
maximum growth rates of coloured single crystals other constituents. Amorphous pyrogenic silica is
of corundum are increased. Furthermore, they suitable as a source of SiO, [893, whilst a gel
reached good results in crystal growth with pow- method seems also ideal for obtaining homoge-
der of the cY-modification instead of y-alumina. neous silicate materials [86].
Purification of the powder material is the first For the growth of yttrium orthovanadate,
step in the feed production process [30,48,46]. Popov worked with powders obtained directly by
Suitable rutile feed powder can be obtained by precipitation from an aqueous solution of potas-
the calcination of the oxalate [27]. For rutile sium vanadate and yttrium nitrate [140]. Merker
production there is another method which pro- developed a process for the growth of metal
duces amorphous, spherical, and very fine parti- titanates, in which the double salt nickel titanium
cles of 30 nm average diameter by thermal hydro- sulphate was calcined at temperatures between
lysis of Ti(C,H,OH), vapour carried by helium at 1100 and 1500°C to form the nickel titanate [1631.
temperatures in the range of 300 to 600°C [162]. For the growth of the alkaline earth metati-
Barta developed methods to obtain high quality tanates, Barta [113] worked with the coprecipi-
Sc,O, [48] or Be0 [46] feed material by chemical tated oxalates. The danger of hydrolysing the
methods working with scandium chloride and ox- Ti(IV) during the precipitation has to be mini-
alate and beryllium sulphate, respectively. Suit- mized by optimizing the processing conditions,
able NiO powder was obtained by pyrolysis of for this purpose an initial oxalic acid solution of
NiCO, [361. For the growth of gallium oxide by 2M, molar ratios of Ti4+ to (COO):- between
the Verneuil technique the available c-phase was 1: 2 and 1: 3 and a maximum temperature of
found to be unsuitable for crystal growth because precipitation of 70°C are shown to be suitable
322 M. Ueltzen / Verneuil flame fusion process: substances

11131. Bednorz and Miiller [1181 worked on the plasma burners. In this way the area of interest in
system LaAlO,-SrTiO, and produced powder by the Verneuil process has been extended also to
coprecipitation from an aqueous solution of ni- non-oxide substances as it is shown in table 2. An
trates with ammonium carbonate as the precipi- overview of this field is given, e.g., by Brice
tant. To compensate for evaporation losses durr [172,173], Laudise [174] and Wilke and Bohm
ing the growth process, the correct ratio of the [175].
metal atoms in the feed can be made to differ
from the required ratio in the crystal.
Finally, it should be mentioned that processing 5. Materials processing
the feed material is a crucial point in flame fusion
growth. It is well known that the quality of the The flame fusion process is not only applicable
crystals depends strongly on the quality of the to the field of crystal growth. For instance, be-
used powder. For this reason, the powder prepa- cause of the geometry of the process, high tem-
ration techniques for industrial crystal growth are perature gradients at the liquid-solid phase
often commercial secrets and the literature does boundary are possible and this feature has been
not provide a complete index of those methods. employed in the textured growth of eutectics.
Borodin et al. [214] worked on the system
Al,O,-ZrO, and produced boules with an inter-
4. Technical developments esting microstructure containing tubular patterns
of ZrO, in an alumina matrix. Savitzky and
The basic Verneuil burner types are reviewed Burkhanov [212] published similar results in the
by Falckenberg [164]. systems tungsten-carbon (W-W,C eutectic) and
The laser technique opened new possibilities niobium-carbon (Nb-Nb,C eutectic) grown by a
for the growth of oxide crystals. However, alter- modified plasma Verneuil process.
native crystal growth techniques had already pro- Another useful feature of the process is that
vided large crystals of high quality by the time after passing the flame, the feed material is
that it was proposed so that the activities on molten. If the material is collected below the
flame fusion growth decreased at the beginning flame, spherical powders or hollow spheres are
of the 1970s. Today, there is a prejudice against produced [215,216] which can be utilized in ce-
Verneuil’s process, that only small size single ramic technology [ 177,121]. Furthermore, spheri-
crystals of inferior quality can be grown. It is cal powders are used for the understanding of
more difficult to control gas flows than electric colloid dispersion or as a model substance for
power and this undoubtedly restricted electronic chromatographic adsorption [217,218]. Other
automation of the flame fusion process. But in fields of interest are heat capacitors made of
the last 10 years, a fully automated computer- metal oxides, electrochemistry and catalysis [219],
controlled flame-fusion crystal growth (CFG) pro- artificial bones [2181 and aerosol research 12201.
cess has been developed by Droste [165]. This has Another area of interest is the processing of
yielded high quality crystals, e.g. of alumina and glass by flame fusion [221,222]. According to a
strontium titanate for use in optics, as laser crys- patent from 1936, quartz glass can be produced
tals, and high T, substrates. by a modified Verneuil process working with a
Other developments have been aimed at spe- mixture of oxyhydrogen and a gaseous hydrolyz-
cial applications for crystals. Thus, it is possible able silicon compound which reacts to form silica
to grow single crystals as tubes [166-1691, thin in the flame. On the top of a ceramic rod posi-
rods [19,17,170] and large area plates 1171,241 by tioned in the flame, quartz glass is produced in a
the Verneuil technique. way similar to the normal crystal growth tech-
Besides the classical Verneuil flame fusion, nique [223-2251. In this manner, also the produc-
there are processes which use other heat sources tion of plates, pipes, rods, discs and crucibles
such as sun light, electric arc, RF plasma, and with high purity, high homogeneity and high di-
Table 2
Crystals grown by modified Verneuil technique

Substance T,,, (“Cl Diam. X length (mm) Means of heating Ref. (year)
Si d6x25 HF plasma [176] (1954)
Al,O,-, ZrO,-, glass-, Arc-melting [1771(1955)
NaCI-, Cu-spheres
Si HF plasma [178] a1 (1957)
ZnSe High-pressure resistance [179] a) (1958)
Si, BaTiO, Plasma torch [180] (1959)
TiO,, Mg-ferrite, Al,O, d(3-6) x(18-50) Arc image [181] (1960)
SiGe ca. 1400 HF plasma [182] b, (1960)
TiC 3250 d3xlO Arc fusion [183] (1961)
MZO, 2050 d(5-15) x (30-90) HF plasma [184] (1961)
ZrO,:Ca 2600-2700
Nb 2420
Cesium iodide HF plasma [185] (1962)
TiC Arc fusion [186] a) (1962)
LaCoO, 1750 Arc-transfer [187] (1963)
TiO,, Also, : Cr, Arc image [188] (1963)
MgFe,O,, ZrO, : Ca
TiO,, Also,, MgO, ZrO,, d5x40 Arc image [189] (1964)
ThO,, HfO,, CaO
NiFe,O, ca. 1200 Arc image [190] =) (1964)
Mg-ferrite Arc image [191] (1964)
TiO,, ZrO, : Ca Arc image [192] (1964)
Refractory crystals 2000 HF plasma [193] (1965)
BaO 1918 d5x20 HF plasma [194] (1965)
SrO 2420
Nb,O,, Ta,O, HF plasma [50] (1965)
TiO, Solar furnace [195] =) (1965)
AlaO,, MgO, ThO,, ZrO, Solar furnace [196] a) (1965)
NiO.Fe,O, > 1500 d(S-8) Plasma torch [197] (1965)
Mn I +xFedA
NiO : Li, oxides of cobalt, iron, d15 Arc-transfer [198] (1966)
titanium, vanadium, nickel ferrite
Also,, SrTiO, Plasma torch [199] ar (1966)
TiB, Arc fusion [200] a) (1966)
W Arc fusion [201] a) (1966)
TaC, --x 3500 d5x25 AC discharge [202] (1967)
HfC
NiO, COO, Fe,O,, Mn,O, DC arc-transfer [203](1967)
A&O,, SrTiO, Plasma torch [204] =) (1968)
Al,O,, Al,O,:Ni, CaWO,, Ce,O,, Arc-transfer [205] (1968)
COO, Fe,O,, NtFe,O,, NrO,
La,O,, Sic, TiO,, VO,, UC, ZrO,
TiO, Plasma Ar-5% 0, [206] (1969)
Ni ferrite Arc image [207] (1969)
Transition element oxides DC arc [208] (1970)
from metal rods
NiO Arc-transfer [209] (1972)
Cr203 2435 Ar plasma [210] (1973)
MgO Arc fusion [211] (1977)
W, MO, Re, Nb, NbC, Tic, > 4000 d(30-50) Plasma torch [212] (1978)
HfC, W-W,C, Nb-Nb,C eutectics
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(La,Sr),CuO, Laser [149] (1988)
YBa,CusO,_, 1100 Laser [150] (1989)
‘) Cited after Wilke and Bohm [175].
b, Cited after Brice [173].
‘) Cited after Laudise [174].
324 M. Ueltzen / Verneuil flame fusion process: substances

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