ISSN 2071-4807
The publication of the journal is supported by
SIA "P&M-Invest" Ltd and INEOS RAS
Volume # 2(9), March - April 2000 — "Nitrogen trifluoride (NF3): Production and purification "
Back to volume # 2(9) , March - April 2000

Fluorine Notes, 2000, 9, 1-2

Nitrogen trifluoride (NF3): Production and purification

T. Fiodorova, S. Igoumnov, V. Kornilov

1. Introduction

NF3 is a toxic gas, inert under normal conditions , odorless in the absence of admixtures. At an elevated temperature it is a strong oxidizer comparable with fluorine.

General constants:

Boiling point, oC -129 (1), -129.1 (2)
Melting point,oC -206.8 (1), -208.5 (2)
Liquid density,g/cm3 - 1.533 (1)
Evaporation heat, cal/mol- 2769 (1)
Melting heat, cal/mol - 95.1 (1)

Due to easy handling at room temperature, NF3 has advantages compared with fluorine and is used as a stable fluorinating agent and has a wide application in high-energy chemical lasers, at dry etching in production of semiconductors, as a filling gas in lamps to prolong their durability and increase brightness, as a detergent gas in CVD apparatuses ( chemical gas-phase precipitation) (3,4,77).

2. Methods of NF3 production

For the first time, NF3 was produced by O.Ruff et al. in 1928 by electrolysis of melt anhydrous NH4* HF at 125oC, voltage of 7-9 V, current of 10 A in a copper electrolytic cell on a carbon anode (5).

This method was assumed as a basis for modern technologies to produce NF3, the second industrial method is direct fluorination of ammonia.

Paper (6) presents a review based on publications right up to 1984 including data on methods of NF3 production, purification, reactions with elements, organic and inorganic compounds and also its molecular properties, spectra, thermodynamic constants etc. That is why the present review considers only publications from 1983 y.

2.1. Electrolytic methods to produce NF3

General data (6)

Electrolysis of NH4F*(1,1-1,8)HF melt is a main method to produce NF3 on an industrial scale. Carbon materials and nickel are used as anode materials each of them has own merits and demerits. Carbon materials contrary to nickel are not liable to anodic dissolution, but during their use there are observed anode polarization ( anodic effect), anodic corrosion and contamination of the goal product with carbon tetrafluoride. The process is described by the following equation:

NH4F*2HF NF3 + 3H2

or

2NH4F*HF NF3 + NH4F + 3H2 (7)

When carbon-containing materials of the anode are used, N2, N2F2, N2F4, NHF2, nitrogen oxides, oxygen and CF4 are formed together with NF3 and H2.

The optimal process parameters are as follows:

Temperature 100-120oC

Current density 0.12-0.15 A/cm2

NF3 current efficiency ~70%.

The electrolysis process is dangerously explosive due to the formation of a mixture of NF3 with hydrogen and other components of electrolysis gas in the cell. To decrease the danger , the anodic and cathode spaces are separated with a diaphragm or the NF3 concentration is kept beyond the bounds of explosiveness by nitrogen introduction into the cell.

Improvement of the electrolysis process

Within the period under review, a number of problems can be chosen which attracted intensive efforts of Japanese companies, particularly of Mitsui Chem. Inc.

  1. Problems concerned with increasing safety of the electrolysis process owing to prevention of mixing anode and cathode gases.

    2. This problem can be solved by the following measures:

    a) electrolytic cell modernization including

  • separation of an anodic and cathode cells with fluoropolymer diaphragm (8)
  • cell coating with a polymer resistant at temperatures above 140oC in places of contact with the melt and synthesis gases (9)
  • certain location of the cell elements (electrodes, the diaphragm, the head):

-the electrodes are placed below the diaphragm base (10) the electrodes are placed at a distance of 30-200 mm from the separating diaphragm (11)

-the electrodes, head and electrolyte surface are installed at a certain distance from each other (12,13)

-two-level arrangement of the electrode cells preventing mixing anodic and cathode gases (14)

b) a number of engineering approaches after the ending of NF3 formation:

    • continuous or periodical arrangement of a potential between the anode and cathode (16)
    • pressure control at gas-carrier supply into the anodic and cathode cells (15)
    • purge with inert gas of the anodic cell equipped with a special nipple joints for gas output and input after the electrolysis stop till its activation (17)
  • Problems concerned with the formation of carbon tetrafluoride difficult to isolate from NF3 and with the anodic effect in case of the use of carbon-containing materials for the anode. The following ways are used to solve these problems:
    • keeping of the water concentration in the electrolyte within 0.01-1%, that is attained by water removal or addition of the starting material in amount of 0.1-10wt.% continuously or periodically (18). It is possible to decrease the water amount and prevent the anodic effect and also formation of CF4when the starting electrolyte is produced from dry gaseous NH3 and HF (19):
    • to carry out the process at a current density above 50mA/cm2 (20)
    • to use a high-strength anode:

    -with the resistance to bending of over 1000kg/cm2 (21);

    -with the resistance to bending of over 50 MPa, current density of 4-30 mA/dm2 and the ratio of HF/NF4F in the electrolyte of 1-3 (22). The anode is made of porous carbon;

    -with the resistance to bending of over 50 MPa, current density of 50 mA/cm2 max, potential between the cathode and neighboring anode of 6V max, quantity of electricity per 1 cm2 of the anode surface of over 500 coulomb (23);

    -with the resistance to bending of over 50MPa, porous anode containing fluorides of Li, Na, Al, Mg, Ca, Ni. The process is carried out at a current density of 4-30 mA/dm2and a ratio of HF/NH4F equal to 1-3 (24).

    • to carry out the process under control of pressure on the anode in dependence of which a necessary current density is provided. (25).
  • When metal anodes are used, their dissolution takes place with the formation of metal salts resulting in passivation of the anode and NF3 yield decrease.

        • To increase the NF3 yield it was proposed:

    • to remove salts formed on the anode (26)
    • to carry out forced convection of the electrolyte suppressing the formation of the salts (27)
    • to use anodes made of special electrode composition produced by sintering Ni-containing oxides with coating of disperse nickel or nickel powder. The temperature of the process is 100-140oC, the ratio of NH4F/HF in the electrolyte is 1-3 (28).
  • Increase in NF3 purity produced during the electrolysis process.

      • -To increase the purity of NF3 , it is necessary to use the starting material of high purity produced from gaseous NF3 of over 99.5 wt. % purity and HF of over 99.8 wt.% purity, nickel electrodes should have purity of 98.5 % min (29,30) or 99.5% min (31).

      -The starting NH4F contains 50 ppm of carbon maximum (32)

    2.2. Investigation of possibility to produce NF3 using binary systems of electrolyte.

    German researchers made attempts to produce NF3 in a higher yields using compounds with a higher valence as an additional nitrogen-containing component , for example hydrazine difluoride in NH4F*HF melt (33).

    This attempt was not crowned with success since the following reactions take place on the anode in case of hydrazine use:

    3N2H4 4NH3 +N2

    N2H4 N2 + 4H+ + 4e-

    Another direction of the investigation was possibility to use additives to NH4F*HF system with the purpose of simultaneous production of NF3 in a higher yield and a different process product. Sulfamoil fluoride H2NSO2F was taken as the additive (34,35).

    H2NSO2F*NH4F8*HF system behaved as a binary electrolyte and they failed to increase the current yield. Simultaneously it was possible to obtain NF3 from NH4+ and SO2F2 from H2NSO2F, at the same time increase in the H2NSO2F quantity resulted in an increase in SO2F2 yield but not NF3.

    Similar behavior of NH4F*HF systems with additives of NH4N(SO2F)2 and (NH2)2SO2 was observed (36).

    2.3. Doshisha University (Kyoto) investigations.

    In the middle 80-s experts of Doshisha University continued a work started in the 60-s by N.Watanabe et al. devoted to the reactions taking place during electrolysis of salt melts with use of carbon-containing anodes and platinum reference electrodes. The purpose of the work was to determine the optimal conditions of NF3 formation.

    Further study of electrolysis of KH2F2- RNH2 systems, where CH3CONH2 and HCONH2 were used as RNH2, on an amorphous carbon electrode at 120oC has shown that the anodic effect was observed at a current density of 3-20mA/cm2 and a film of carbon polyfluoride (CxF)n was formed on the anode. 1% LiF addition prevented the anodic effect but reduced the yield of NF3 and the water content in the melt. The maximum NF3yield of 50.9% was obtained at a current density of 5.3 mA/cm2 and 4 mol% of HCONH2 additive (37,38). The same yield under similar conditions was obtained when a glossy anode was used (39).

    An addition of urea to a system of KH2F3 was studied earlier (40).

    An addition of urea to a different system of NH4F-HF-KF gives the same results, i.e. an increase in the NF3 current efficiency due to removal of water which is consumed for urea hydrolysis and COF2 forming in the process. The maximum content of NF3in the anode gas is 87% (41).

    Later on investigations were carried out using NH4F*2HF melt and a nickel anode.

    A possibility to improve the process parameters due to introduction of such additives as NH4NiF3,(NH4)3FeF6 and AlF3 to the electrolyte has been tested.

    If the maximum NF3 yield attained 66% without additives at the anodic dissolution of 3%, then an addition of 0.1mol% of the most effective complex of NH4NiF3 reduced the anodic dissolution to 1%, but the NF3 yield reduced to 60% also (42,43,44). The process with the use of NH4NiF3 has been patented (45).

    CsF (46,47) and LiF (48,49) were used as additives. The additives of these salts reduce the anodic dissolution and increase the NF3 yield. The processes using CsF and LiF have been patented (47,49).

    Further studies on the effect of fluorides such as KF,MgF2,NaF, AlF3, CsF and LiF confirmed the effectiveness of CsF and LiF additives and showed that KF reduced the NF3 yield and stimulated the anodic dissolution (50,51).

    A search for metal workable in NH4F*HF*CsF melt has found that Al, Fe, Mo, Nb, Sn, Ta and Ti are subjected to vigorous dissolution. Ag, Co, Cu, and Zn are also unusable because of passivation preventing from current passage.

    Nickel was found the most acceptable metal for the anode, and also Monel , one of its alloys (52). Electrodes made of Ni-NiO1-x composite produced by HIP ( hot isotactic pressing) method were also studied. The anode made of 10% composite was covered with a thick layer of oxides with infrequent porouness that prevented the anode from dissolution and increased the NF3 yield. An anode made of 20% composite has these parameters much worse. The anodes operated in NH4F*2HF melt (53).

    An anode made of a different material, carbon impregnated with lithium fluoride, was studied in systems of NH4F-HF, KF-NH4F-HF, CsF-NH4F-HF. The yield of NF3 on these anodes is lower than that on nickel ones (53).

    Further study of the anodic reactions on the nickel anode in melt of CsF-NH4F*HF at 50-80oC allowed to conclude that an increasing the potential resulted in change of the anodic reactions and four zones were separated in dependence on the voltage:

    0-1V ( compared with H2 standard electrode): nickel anodic dissolution

    1-3V :deposition of Ni (II) compounds containing oxides (passivation)

    3-5V : Ni(II) oxidation to Ni(III) and/or Ni(IV)

    over 5V: proper NF3 fluorination

    The anode gas is composed of NF3 and N2 with a small additive of O2,N2O, N2F2, N2F4 (55). A similar picture is observed in melts of (CH3)4NFm*HF and (CH3)4NFm*HF + 50% CsF*2HF, where m=3,5+0.5n (n=1-4).

    Here also 4 zones are seen. An oxidized layer is formed at a potential above 4V and is composed of NiF2, fluorides with high oxidation level and a small quantity of oxides of different valence (56). Paper (57) describes a mechanism of fluoride films formation on the anode. This phenomena and possible effect of fluoride layers on the fluorination process have been reviewed in paper (54).

    3. Ammonia direct fluorination

    Ammonia fluorination in NH4F*HF melt is far more practically feasible process than gas-phase fluorination . That allowed Air Products and Chem. to implement this process on an industrial scale and produce the product of 99.5% purity (6).

    Later on research in this field was directed to

    1. expansion of a source of raw materials
    • (NH4)3AlF6, (NH4)2SiF6 and (NH4)2NaAlF6 were proposed as a starting solid complex. Their interaction with fluorine is conducted at a temperature below 150oC. The product obtained has a purity of 98.5% (58)
    • metal fluorides in a mixture with ammonium salt at fluorination with elemental fluorine diluted with nitrogen give NF3 in 96.9% yield (59)
  • search of solutions on prevention of clogging apparatus
    • to produce NF3 by gas phase method at a ratio of F2/NH3 equal to 3-20, it is envisaged to place a reactor in a heating area at 80-250oC (60)
    • two plates are placed in the reactor with a gap of 0.1-10cm (61)
    • fluorine and ammonia used in the gas phase process are charged through a spiral along the inside reactor wall for mixing and interaction. The formation of NH4F2 resulting in clogging is prevented (62).

    A processing line with circulation of a melt containing ammonia, metal fluoride and HF has been patented. The processing line includes the following equipment through which the melt circulates: an electrolizer to produce fluorine and hydrogen, a reactor for NF3 production and 2 apparatuses- solubilizers located between them, one apparatus at the output of the melt from the electrolyzer and the second one at the input. Gas-carrier together with ammonia and fluorine respectively are charged into these apparatuses to keep the ammonia and HF concentration constant in the melt. Fluorine mixed with the gas-carrier comes to the reactor where it reacts with the melt to form NF3 (63).

    Paper (64) suggests to carry out interaction of elemental fluorine with ammonia complex NH4F*HF, (NH4)1-4MF2-8*nHF ( where M is an element of I A-V A group, I B-VII B group and VIII group) at mixing of the melt complex with a turbine-type mixer.

    4. NF3 purification methods

    Modern electronic industry makes high demands for NF3 purity right up to 99.999% in which connection a great attention is paid to NF3 purification.

    Methods for NF3 treatment for removal of acid and hydrolyzable admixtures and difluorodiazine, N2F2, have been described in (6). N2F2 was removed by decomposition over a nickel-containing catalyst at 240oC, for example in a nickel pipe filled with nickel balls or other nickel packing. In this case the content of N2F2is reduced from over 0.1% to less than 0.01%.

    NF3 catalytic purification from N2F2with nickel-containing compounds was further developed in the work of Mitsui Toatsu Chem. Inc. . They used heating NF3 raw at 150-600oC in a vessel covered with nickel fluorides. The vessel coating was made by its treatment with fluorine (66, 67, 68, 69, 70, 71). To increase the purification level, the vessel may be filled with fluorides (69-72), for example with fluorides of nickel or calcium (74).

    To purify NF3 from N2F2 and/or OF2 it is suggested to use other fluorides:

    • tablets made from NaF melt and polyvinyl alcohol preheated at 850oC before use (75)
    • silicon fluorides after heating at a temperature over 600oC (65)

    Sorbents are widely used for NF3 purification. A process with their use is carried out in adsorption or chromatographic regime.

    • when NF3 containing 1.7% of N2F2 is contacted silica gel, the content of N2F2 is reduced to 20ppm (76)
    • silica gel preheated and preliminarily dried at a temperature of 150-300oC effectively removes N20 and CO2 at a temperature of 125oC (68,70,77)
    • anhydrous aluminum oxide (Al2O3) at 250-900oC and the same adsorption temperature removes N2O and CO2 (69,71,79)
    • activated carbon after preliminary removal of acid admixtures from NF3 purifies it completely from N2F2 and N2F4 (78,83)
    • SiO2 with interstices of 3-10 mm is applied for removal of nitrogen oxides without NF3 losses (80)

    Purification with use of natural and synthetic zeolites (81) is also wide spread.

    Before use, zeolites are preheated in a nitrogen flow at a temperature of 270-700oC (81,85,86). For their reuse, the heating is conducted step-by-step, first at 50-200oC, then at 250-700oC (87,88). To ensure the uniform heating of zeolites, metal perfluorinated disc-shaped plates are inserted in the zeolites (89). A purification temperature with use of zeolites is 125-110oC.

    The following admixtures are removed by means of zeolites:

    • N2O and N2F2, in this case it is recommended to carry out additional treatment of zeolites with solutions of sodium salts of organic and inorganic acids with subsequent heating at 250-700oC (82)
    • N2O and CO2 (90,91,92,93,86)
    • water for which removal natural (93) and synthetic (94) zeolites of 3A type are used

    To separate NF3 and CF4 a chromatography method is applied using zeolites of 3A type either containing 1-10% of water (84) or preliminarily wetted with water and heated for 16 hours at 300oC in inert medium of chabazite or zeolite of 5A type with the pore surface of 4.4-4.8 A. The charge of the flow to be separated is executed in a pulse regime. Purification of the separated gases reaches 99.99% (95).

    SiO2 adsorbents, carbon molecular sieves, Al2O3, macro-cross-linked polymers, kieselgur, active carbon, aluminosilicates and zeolites containing also chemosorbents for decomposition of admixtures may be used for sorption storage of gases in a special adsorption-desorption apparatus. A gas to be desorbed is charged directly to a CVD apparatus or a laser plant (107-109).

    Low-temperature rectification in the presence of a third component (He, Ar, Ne etc.) is used for purification of NF3 from N2F2, CO2, O2,N2 (96-98). A complex of procedures for NF3 purification including sorption purification and rectification in columns of middle and low pressure has been patented (99).

    A method to purify NF3 from CF4 by azeotropic and extractive low-temperature rectification to the content of admixtures of 10 ppm was described in (111).

    The following methods of NF3 purification were also described:

    • to purify from HF and OF2, the raw gas is first washed with water or a solution of NaOH, then it is treated in a scrubber with aqueous solution of Na2S2O3, HI or Na2S (100)
    • application of a reactive micromatrix containing organo-metalic compounds allows to reduce admixtures to ppb level and even lower (101)
    • to remove water from a number of gases including NF3, a process including distillation of water and its separation from the gases was patented (102)
    • to remove N2F2, purification by UV radiation treatment with subsequent contacting the gas with adsorbents was suggested (103)
    • processes of NF3 separation from a gas-diluent by means of selective membranes are described in (104,105)

    Usually the purified NF3 is stored in cryogenic tanks (91,92) including tanks joined to a heat exchanger for NF3 condensation (106).

    Gases containing NF3 and admixtures are fractionated by gas chromatography method and analyzed by IR-spectroscopy (46), gas chromatography identification of NF3 traces is also known (110)

    The water content in NF3 less 50 ppm may be determined by laser spectroscopy (112).

    References

    1. Kirk-Othmer, Encyclopedia of Chemical Technology, 1980, v.10. p. 768
    2. Kratkaia khimicheskaya encyclopedia, 1966, v.5, p. 579, Izd. "Sovetskaya encyclopedia"
    3. Ullmann's Encyclopedia of Industrial Chemistry, 1988. v. A II. p. 339
    4. J. Fluor. Chem., 1985, v. 27, n. 1, p. 23-33
    5. 0. Ruff, I. Fisher. F. Luft, Z.anorg. Chem.,1928, v.172, 417-425
    6. Gmelin Handbook, 1986, v.4, p. 171-231
    7. A.Zemljic, B.Druzina, A.Smallm, Kern. Ind., 1986,v 35. N 5, p. 277-279; CA. 1986, v.105. 87396
    8. T.Iwanaga, H.Momotake, A.Tasaka, JP. Appl. 88-130790, 1986/88, Mitsui Toatsu Chem Inc, CA,1989,v.110,15084
    9. A. Mitsumoto. A.Aritsuka ,I.Harada, JP. Appl. 94-88267, 1992/94, Mitsui Toatsu Chem. Inc., CA, 1994. v.121,68148
    10. T.Iwanaga, I.Harada, T. Yamaguchi. JP. Appl. 90-61082. 1988/90, Mitsui Toatsu Chem.Inc.,CA,1990,v.113. 200125
    11. N.Iwanaga, T.Yamaguti, N. Fujieda and others, EP 424727, 1989/91, Mitsui Toatsu Chem. Inc., CA, 1991. v. 115, 122501
    12. N. Iwanaga, T. Yamaguti, N. Fujieda and others, US Patent 5054156. 1989/92, Mitsui Toatsu Chem.Inc.. CA, 1992,v.116, 223788
    13. T. Iwanaga. T. Kuroda, JP. Appl. 92-160176. 1990/92, Mitsui Toatsu Chem.Inc.,CA. 1993. v.118. 156854
    14. G. Tarancon, US Patent 5779866, 1996/98, Florida Scientific Lab. Inc., CA, 1998, v. 129, 128237
    15. I. Harada. T. Iwanaga, JP. Appl. 90 232386, 1989/90, Mitsui Toatsu Chem. Inc., CA, 1991, v. 115, 17581
    16. M. Aritsuka. T. Iwanaga, JP. Appl. 92 32592, 1990/92, Mitsui Toatsu Chem.Inc., CA, 1992, v. 116, 223786
    17. M. Aritsuka, T. T. Nishitsuji, T. Iwanaga, JP Appl. 92 09488, 1990/92, CA, 1992, v. 116, 183525
    18. M.Aritsuka. T.Ivanaga, H.Hotconohara, JP.Appl. 90-263988, 1988/90, CA. 1991, v.115,37512
    19. M. Zaike, T.Iwanaga, JP. Appl. 92-56789, 1990/92, Mitsui Toatsu Chem. Inc., CA, 1992, v.117, 200536
    20. M.Aritsuka, A.Mitsumoto, JP. Appl. 93-51778, 1991/93, Mitsui Toatsu Chem. Inc., CA, 1993, v. 119, 58356
    21. M.Aritsuka. T.Iwanaga, A.Mitsumoto, JP. Appl. 92-131391, 1992/90, Mitsui Toatsu Chem.Inc., CA,1994,v.120, 64636
    22. M.Watanabe, Y.Tei, M.Kanamaru, M.Aritsuka, A. Mitsumoto, JP. Appl. 93-70982. 1991/93, Mitsui Toatsu Chem.Inc.,CA, 1993,V.119, 104967
    23. M. Aritsuka, A.Mitsumoto. JP. Appl. 93-51779, 1991/93, Mitsui Toatsu Chem.Inc., CA, 1993, v.119, 58362
    24. N. Watanabe, Y.Tei, M. Kanamaru, M. Aritsuka, A.Mitsumoto, JP. Appl. 93-86490, 1991/93, Mitsui Toatsu Chem.Inc., CA,1993. v.119, 236543
    25. M.Aritsuka. A.Mitsumoto, JP. Appl. 93-51782, 1991/93, Mitsui Toatsu Chem.Inc.,CA, 1993, v.119, 58363
    26. I.Orihara, S.Sato, M.Saito, N.Ono, JP.Appl. 91-236486, 1990/91, Kanto Denka Kogyo Co. Ltd., CA,1992, v.116, 8505
    27. T. Yoshino, H. Kamata, T. Shinozaki, JP.Appl. 96-176872, 1994/96, Mitsui Toatsu Chem.Inc., CA, 1996, v.124,179865
    28. A.Tasaka, M.Aritsuka, T.Iwanaga, A.Mitsumoto, JP.Appl. 96-225976, 1995/96, Mitsui Toatsu Chem.Inc., CA, 1996, v.125, 280153
    29. T.Shinozaki, Y.Hirata, JP.Appl. 96-134675, 1994/96, Mitsui Toatsu Chem.Inc.,CA, 1996, v.125,126099
    30. T.Shinozaki, Y.Hirata, JP.Appl. 96-120474,1994/96, Mitsui Toatsu Chem. Inc., CA,1996, v.125, 62494
    31. T.Shinozaki, T.Yoshino, JP. Appl. 97-86909, 1995/97, Mitsui Toatsu Chem. Inc., CA., 1997, v.127, 20515
    32. H.Hokohara, T.Iwanaga, I.Harada, T.Yamaguchi and others, JP.Appl. 89-191792, 1988/89, Mitsui Toatsu Chem.Inc., CA,1 990, v.112, 13434
    33. P.Sartori, DE off. 3722163, 1987/89, Kali-Chemie AG, CA, 1989,v.110,162522
    34. P.Sartori, K.D.Lattasch, J. Fluor. Chem.,1992,v.57(1-3), p. 113-119
    35. P.Sartori, C.Juenger, K.D.Lattasch, DECHEMA Monogr.,1992, 125. (Electrochem. Stoffgewinnung Grundlagen Verfahrenstech.) 233-242, CA. 1992. v. 117.159540
    36. P.Sartori, K.D.Lattasch, J.Fluor.Chem..1995.V.74, n.1.p.137-139, CA, 1995, v.123, 269235
    37. A.Tasaka, H.Sakaguchi, R. Aki, H.Ihara and others, J.Fluor.Chem.,1985, v.27, n.1, p.23-33
    38. A.Tasaka. H.Sakaguchi, T.Yamamoto, Proc. Int. Symp. Molten Salt Chem. Technol., 1st, 1983,305-308, CA.1985,v.102,139700
    39. A.Tasaka, H.Sakaguchi, H.Ito, N, Norimuna, Nippon Kagaku Kaishi, 1988, n.6, 873-880, CA.1988,v.109,199844
    40. A.Tasaka, H.Watanabe, Denki Kagaku Oyobi Kogyo Butsuri Kagaku, 1981, 49, n.8, 511-516, CA,1981,v.95,158699
    41. A.Tasaka, H.Ito, H.Kobayashi, Nippon Kagaku Kaishi, 1985, n.10, 1785-1804, CA, 1985, v.103, 223152
    42. A.Tasaka, H.Kabayashi, M.Hori and others, Proc-Electrochem Soc..1987, 87-7 (Proc. J. Int. Symp. Molten salts), 949-958,CA, 1987,v.107,163987
    43. A.Tasaka, M.Negami, K.Nagasaki and others, Proc.Electrochem Soc.,1994, 94013. (Molten Salts), 601-608, CA, 1995,v.122,40888
    44. A.Tasaka, H.Kobayashi, M.Negami and others, J. Electrochem Soc.,1997, v.l44, n.1,192-197,CA,1997, v.126, 244038
    45. A.Tasaka, H.Nakayama, JP.Appl. 88-274789, 1987/88, Showa Denco K.K., CA, 1989.v.110,143550
    46. A.Tasaka, K.Mizuno, A.Kamata, K.Miki, J.Fluor.Chem.,1992, v.57 (1-3), 121-130
    47. A.Tasaka, T.Tateno, JP.Appl. 91-104891, 1989/91, Morita Kagaku Kogyo Co. Ltd., CA,1991,v.115,169018
    48. A.Tasaka, T.Osada and others, Proc.-Electrochem. Soc.,1996, 96-7 (Molten Salts), 144-151,CA,1996, v.125, 259549
    49. A.Tasaka, M. Aritsuka, T. Iwanaga, A. Mitsumoto, JP. Appl. 96-225973, 1995/96,CA, 1996, v. 125, 280152
    50. A. Tasaka, M. Yamanaka, T. Osada, Proc.-Electrochem. Soc. , 1997, 97-15 ( Electrochemistry in the preparation of Fluorine and its compound), 144-157, CA, 1997, v. 127, 254450
    51. A. Tasaka, T. Osada, M. Kobayashi and others, J. Fluor. Chem.,1998, v.87, n.2, p.163-171
    52. A. Tasaka, K. Mizuno, A. Kamata, Mater. Sci. Forum, 1991, 73-75 ( Molten Salt Chem. Technol.), 603-608
    53. A. Tasaka, H. Oshida, Y. Suzuki and others, Proc.-Electrochem. Soc.,1998, 97-28, 109-118, CA, 1998, v.128, 276312
    54. A. Tasaka, T. Kawagoe, A. Takuwa, M. Aritsuka, J. Electrochem. Soc., 1998, v. 145, n. 4, p. 1160-64, CA, 1998, v.129, 20828
    55. A. Akimasa, K.Mizuno,A. Kamata and others, Proc.-Electrochem. Soc., 1992, 16 (Proc. Int. Symp. Molten Salts, 8th,1992),564-73
    56. A. Tasaka,T.Yachi, T. Makino and others, Proc.-Electrochem. Soc.,1998, 98-11 (Molten Salts XI), 658-666, CA, 1999, v.130, 58381
    57. A.Tasaka, Y. Tsukuda,S. Yamada and others, Electrochem. Acta, 1999, v.44, n. 11,1761-1769, CA, 1999, v.130, 202125
    58. M. Aramaki, Y. Kobayashi, T. Nakamura, DE off. 3435298, 1983/85,Central Glass Co. Ltd., CA, 1985, v.102, 206098
    59. I. Orihara, S. Sato and others, JP.Appl. 91-232710, 1990/91, Kanto Denka Kogyo Co. Ltd., CA, 1992, v.116, 109560
    60. M. Shimizu, JP. Appl., 90-255512, 1989/90, Asahi Glass Co. Ltd., CA, 1991, v.114, 84845
    61. M. Shimizu, JP. Appl., 90-255511, 1989/90, Asahi Glass Co. Ltd., CA, 1991, v.114, 84846
    62. K. Katsumi, K. Okana, T. Mukono, T. Kurada, JP. Appl. 93-105411, 1991/93, Onoda Cement Co. Ltd., CA, 1993, v.119, 99212
    63. G. Tarancon, US 5628894,1995/97, Florida Scientific Lab., CA, 1997, v.127, 25046
    64. D. G. Coronell, T.H.L. Asiung, H.P.Withess, US 5637285, 1996/97, Air Prod. And Chem. Inc., CA, 1997, v.127, 83493
    65. T. Nishitsuji, M. Aritsuka, JP. Appl. 92-198006, 1990/92,Mitsui Toatsu Chem Inc., CA, 1992,v.117, 236701
    66. I. Harada, H. Hokonohara, T. Yamaguti, EP Appl. 337294, 1988/89, Mitsui Toatsu Chem. Inc., CA, 1989, v.111, 236120
    67. I. Harada, H. Hokonohara, T. Yamaguti, JP. Appl. 89- 261206, 1988/89, Mitsui Toatsu Chem. Inc., CA, 1990, v.112, 237761
    68. T. Nishitsuji, T. Iwanaga, I. Harada, JP. Appl. 90 164707, 1988/90, Mitsui Toatsu Chem. Inc., CA, 1990, v.113, 214867
    69. T. Nishitsuji, T. Iwanaga, N. Koto, JP. Appl. 90-22111, 1988/90, Mitsui Toatsu Chem. Inc., CA, 1990, v.113, 81617
    70. T. Nishitsuji, T. Iwanaga, I. Harada, JP. Appl. 90 164708, 1988/90, , Mitsui Toatsu Chem. Inc., CA, 1990, v.113, 214868
    71. T. Nishitsuji, T. Iwanaga, I. Harada, JP. Appl. 90 18309, 1988/90, Mitsui Toatsu Chem. Inc., CA, 1990, v.113, 135114
    72. T. Suenaga, JP. Appl. 90-116216, 1997/99, Central Glass Co. Ltd.
    73. I. Harada, H. Hokonohara, T. Yamaguchi, JP. Appl. 89 261208,, 1988/89, Mitsui Toatsu Chem. Inc., CA, 1990, v.112, 237762
    74. I. Harada, H. Hokonohara, T. Yamaguchi, JP. Appl. 92 275909, 1991/92, Mitsui Toatsu Chem. Inc., CA, 1993, v.118, 41816
    75. T. Nishitsuji, M. Aritsuka, JP. Appl. 92 12010, 1990/92, Mitsui Toatsu Chem. Inc., CA, 1992, v.116, 154912
    76. I. Harada, T. Iwanaga, H.Homotake, JP. Appl. 88 151608, 1986/88, Mitsui Toatsu Chem. Inc., CA, 1988, v.109, 131692
    77. T. Nishitsuji, T. Iwanaga, I.Harada, JP. Appl. 90 153809, 1988/90, Mitsui Toatsu Chem. Inc., CA, 1990, v.113, 155343
    78. F. Morikawa, E. Hirai, JP. Appl. 95 330316, 1994/95, Nissan Chem. Ind.Ltd., CA, 1996, v.124, 236439
    79. T. Nishitsuji, T. Iwanaga, N. Koto, JP. Appl. 89 261209, 1988/89, Mitsui Toatsu Chem. Inc., CA, 1990, v.112, 237763
    80. T. Nishitsuji, T. Iwanaga, M. Aritsuka, JP. Appl. 91 275507, 1990/91, Mitsui Toatsu Chem. Inc., CA, 1992, v.116, 154922
    81. T. Shinozaki, H. Kamada, JP. Appl. 96 91812, 1994/96, Mitsui Toatsu Chem. Inc., CA, 1996, v.125, 37429
    82. T. Nishitsuji, T. Iwanaga, M. Aritsuka, JP. Appl. 92 175211, 1990/92, Mitsui Toatsu Chem. Inc., CA, 1992, v.117, 174553
    83. K. Kamatura, K. Sugano, H. Nakayama, JP. Appl. 86 247609, 1986/86, Showa Denco K.K., CA, 1987, v.106, 122463
    84. T. Suenaga, T. Fujii,Y. Yobayashi, JP. Appl. 91 208806, 1990/91, Central Glass Co., CA, 1991, v.115, 259374
    85. M. Aritsuka, N. Iwanaga, EP 366078, 1988/90, Mitsui Toatsu Chem. Inc., CA, 1990, v.113, 43437
    86. M. Aritsuka, N. Iwanaga, JP. Appl. 92 144905, 1990/92, Mitsui Toatsu Chem. Inc., CA, 1992, v.117, 114704
    87. N. Fujieda, T. Yamaguchi, JP. Appl. 92 187510, 1990/92, Mitsui Toatsu Chem. Inc., CA, 1992, v.117, 194705
    88. N. Fujieda, T. Yamaguchi, M. Aritsuka, JP. Appl. 92 254404, 1991/92, Mitsui Toatsu Chem. Inc., CA, 1993, v.118, 8944
    89. I. Harada, JP. Appl. 92 228408, 1990/92, Mitsui Toatsu Chem. Inc., CA, 1992, v.117, 254315
    90. I. Harada, T. Nishitsuji, T. Iwanaga, N. Koto, JP. Appl. 90 30609, 1988/90, Mitsui Toatsu Chem. Inc., CA, 1990, v.113, 135203
    91. M. Aritsuka, T. Iwanaga, JP. Appl. 92 77305,1990/92, Mitsui Toatsu Chem. Inc., CA, 1992, v.117, 51883
    92. M. Aritsuka, N. Iwanaga, JP. Appl. 92 77306, 1990/92, Mitsui Toatsu Chem. Inc., CA, 1992, v.117, 51884
    93. P. B. Henderson, C. Coe, T.C. Golden, JP. Appl. 98 259011, 1997/98, Air Products and Chemicals Inc., CA, 1998, v.129, 247238
    94. H. Kasatani, T.Shimada, N. Muranaga, JP. Appl. 96 259206, 1995/96, Japan Pionics, CA, 1997, v.126, 33995
    95. P.B. Henderson, C. Coe, D.E. Foeler, M.S. Benson, US 5069690, 1991, Air Products and Chemicals Inc., CA, 1992, v.116, 50577
    96. H. Harada, H. Momotake, T. Nishitsuji, JP. Appl. 88 306383, 1987/88, Mitsui Toatsu Chem. Inc., CA, 1989, v.111, 117780
    97. H. Hyakutaka, I. Harada, N. Iwanaga, T. Nishitsuji, Appl WO 89 0444 1987/89, Mitsui Toatsu Chem. Inc., CA, 1989, v.111, 216725
    98. H. Yokoma, T. Takumi, F. Mozikawa, JP. Appl. 95 330317, 1994/95, Nissan Chem. Ind. Ltd., CA, 1996, v.124, 180437
    99. T. Nagamuze, EP Appl. 807600, 1996/97, Teisan K.K. Japan, CA, 1998, v.128, 36951
    100. N. Koto, T. Nishitsuji, N. Iwanaga, I. Harada, EP 344612, 1988/89, Mitsui Toatsu Chem. Inc., CA, 1990, v.112, 80491
    101. T.D.Canbria, R.I. Duguid, R. Binder, Proc. - Inst. Environ. Sci.,19992, 38th (vol.1),142-148, CA, 1994, v.120, 248051
    102. K. Nakamura, T.Kijima and others, EP 662339, 1994/95, Osaka Santo Kogyo K.K.
    103. T. Nishitsuji, H. Momotake, I. Harada, JP. Appl. 88 201007, 1987/88, Mitsui Toatsu Chem. Inc., CA, 1988, v.110,32563
    104. J.Chernyakov, T.Hsiao-Ling, A.Schwarz, J.Hsu-Kuang Yang, US 5370779,1996/98, Air Prod. And Chem. Inc., CA, 1998, v.128, 206128
    105. Li Yan-en, I.E.Paganessi, D.Vasallo and others, EP Appl. 853970, 1997/98, L'ais Liquide, CA, 1998, v.129, 150742
    106. M. Aritsuka, N. Iwanaga, N. Fujeda, JP. Appl. 92114910, 1990/92, Mitsui Toatsu Chem. Inc., CA, CA, 1992, v.117, 93130
    107. G. M. Tom, I. V. McManus, W.K. Olander, US 5704965, 194/98, Advanced Technology Materials Inc.,CA, 1998, v.128, 103939
    108. G. M. Tom, I. V. McManus, US 5707424, 1996/98, , Advanced Technology Materials Inc.,CA, 1998, v.128, 116684
    109. G. M. Tom, I. V. McManus, WO Appl. 96 11739, 1994/96, Atmi Ecosys. Corp., CA, 1996, v.125, 24038
    110. H. Ogino, Y. Aomura, T. Suzuki, M.Hatano, Anal. Sci., 1988, v.4, n. 4, 425-426, CA, 1989, v.110, 127698
    111. B.A. Mahler, R.N. Miller., WO 99 24358, 1998/99, C.P.C. Kao DuPont, CA, 1999, v. 130, 326793
    112. I.M. Grizard, P.Mauvais, Proc. ISSM'96 Int. Symp. Semicond. Manuf. 5th , 1996, 325-28, CA, 1999, v. 130, 75441

    Fluorine Notes, 2000, 9, 1-2

    Back to volume # 2(9) , March - April 2000
    © 1998-2025 Fluorine Notes. All Rights Reserved.