GB2075478A - Improvements in or Relating to Cerium Compounds - Google Patents
Improvements in or Relating to Cerium Compounds Download PDFInfo
- Publication number
- GB2075478A GB2075478A GB8112046A GB8112046A GB2075478A GB 2075478 A GB2075478 A GB 2075478A GB 8112046 A GB8112046 A GB 8112046A GB 8112046 A GB8112046 A GB 8112046A GB 2075478 A GB2075478 A GB 2075478A
- Authority
- GB
- United Kingdom
- Prior art keywords
- cerium
- cerium compound
- dispersible
- dry
- oxide hydrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/276—Nitrates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
Abstract
A process for the preparation of a dispersible cerium compound comprises heating a substantially dry cerium (IV) oxide hydrate in the presence of a deaggregating agent to cause deaggregatlon of aggregated crystallites in the cerium (IV) oxide hydrate and produce a dry dispersible cerium compound. The deaggregating agent is an acid species e.g. NO3<->, Cl<-> or ClO4<->. The dry dispersible product may be mixed with an aqueous medium to form a colloidal dispersion and if the dispersion is allowed to dry, a gel.
Description
SPECIFICATION
Improvements in or Relating to Compounds
The present invention relates to compounds and more particularly to cerium compounds.
According to one aspect of the present invention there is provided a process for the preparation of a dispersible cerium compound which comprises heating a substantially dry cerium (IV) oxide hydrate in the presence of a deaggregating agent to cause deaggregation of aggregated crystallites in the cerium (IV) oxide hydrate and produce a dry dispersible cerium compound.
Preferably the deaggregating agent comprises acid species.
It is to be understood that the concentration of deaggregating agent used and the temperature and time of heating is such that the desired degree of deaggregation is effected. The concentration, temperature and time can be determined by experimentation for a particular cerium (IV) oxide hydrate starting material.
By "dispersible cerium compound" as used in this Specification it is meant that the cerium compound is dispersible in aqueous media (e.g.
water or aqueous acid solutions) to give a colloidal dispersion (i.e. a sol). The dry dispersible cerium compound may of course still contain "structural" water.
The term "acid species" as used in this
Specification embraces hydrogen ions, hydroxonium ions and anions which normally accompany hydrogen or hydroxonium ions in acidic conditions (e.g. nitrate ions). Preferably the anion concentration (e.g. NO;) in the dry dispersible cerium compound is controlled so as to facilitate the dispersion of the cerium compound in aqueous media. This control may be effected by controlling the removal of anions by heating.
British Patent Application No. 22835/78 (UKAEA) (to which West German
Offenlegungsschrift 2857146 corresponds) discloses inter alia : "A process for the preparation of an aqueous
dispersion of ceria which comprises forming
a slurry of cerium (IC) hydroxide with water
and an acid, the acid being capable of
causing deaggregation of aggregated
crystallites in the cerium (IV) hydroxide,
heating the slurry for such a time that the pH
reaches a steady value, the quantity of acid
in the slurry being such that the said steady
value of pH is below 5.4, thereby to produce
a conditioned slurry and admixing water with
the conditioned slurry to produce an
aqueous dispersion of cerium".
British Patent Application No. 22835/78 also discloses (page 6 lines 1 to 3) that certain cerium (IV) hydroxides are not easily susceptible to deaggregation in accordance with the invention disclosed therein and additionally the foliowing passage appears at page 6 line 1 8 to page 7 line 2:
"Furthermore, to facilitate deaggregation as
hereinbefore disclosed we believe that it is
preferable that the starting cerium (IV)
hydroxide should not have been heated to
cause any substantial irreversible loss of
water (e.g. heating to > 1 000C) prior to
treatment in accordance with the present
invention.For example we have found that a
starting cerium (IV) hydroxide having 25% by
weight water can be deaggregated in
accordance with the present invention
whereas some samples with 10% by weight
water content were not easily amenable to
deaggregation. Also we believe that the time
and temperature and humidity of any prior
heat treatment of the starting cerium (IV)
hydroxide may affect the susceptibility of the
cerium (IV) hydroxide to deaggregation in
accordance with the present invention".
Thus, British Patent Application No. 22835/78 indicates that it is undesirable to heat cerium (IV) hydroxide to an extent which causes any substantial irreversible loss of water if it is desired to effect deaggregation to give a dispersible product.
Surprisingly in accordance with the present invention a cerium compound which is readily dispersible in aqueous media to give highly concentrated sols may be prepared by a process which involves heating substantially dry cerium (IV) oxide hydrate to give a dry cerium compound.
Cerium (IV) oxide hydrate for treatment in accordance with the present invention can be obtained commercially or, alternatively, can be prepared by any suitable route. For example, it can be prepared from readily available cerium salts, (e.g. of "reagent grade"). The preparation may be by precipitation from a cerium salt.
Thus, for example, as disclosed in British
Patent Application No. 22835/78, high purity cerous carbonate can be dissolved in aqueous nitric or hydrochloric acid to give a neutral solution and then oxidised with NH4 OH/H2 2 to give cerium (IV) oxide hydrate.
By way of further example cerium (IV) oxide hydrate for treatment in accordance with the present invention may be prepared by the conventional routes disclosed at page 1 lines 40 to 61 of B.P. No. 1342893 (UKAEA).
Cerium (IV) oxide hydrate when prepared by usual commercial preparation routes often contains anions (e.g. nitrate ions). With such oxide hydrates if the concentration of the anions is sufficiently high it is not necessary to add additional acid species prior to heating to effect deaggregation and production of a substantially dry dispersible cerium compound in accordance with the present invention.
If, however, the concentration of acid species is too low to effect the deaggregation on heating additional acid species may be introduced to the cerium (IV) oxide hydrate prior to heating (e.g. by the addition of nitric acid).
Examples of anions suitable for use in accordance with the present invention are nitrate anions, chloride anions, perchlorate anions and any combination of these.
The degree of hydration of the cerium (IV) oxide hydrate starting material may vary over a wide range.
By way of example, dry dispersible cerium compounds have been prepared in accordance with the present invention from cerium (IV) oxide hydrate starting materials having respectively 8% water and 60% water. Also by way of example, dispersible cerium compounds have been prepared from oxide hydrate starting materials having other water contents.
It is preferred that the temperature of heating of the cerium (IV) oxide hydrate is in the range 200-4000C and it has been found that heating in the range of 300-3500C is particularly useful in producing dry dispersible cerium compounds which can be dispersed to give highly concentrated sols (e.g. > 600 gl- > (3.5M in
Ce(lV))).
When nitrate ions are used in accordance with the present invention it is preferred that the nitrate/Ce 02 ratio is in the range 0.15 to 0.35 in the cerium (IV) oxide hydrate starting material.
A time ofN1 to 2 hours has been found to be suitable for heating the cerium (IV) oxide hydrate in the range of 2000C to 4500C to effect deaggregation in'accordance with the present invention.
Preferably the nitrate/CeO2 ratio in the dry dispersible cerium compound is in the range 0.05 to 0.25 and a particularly preferred range is 0.08-0.15.
The cerium (IV) oxide hydrate starting material typically can consist of insoluble particles of up to ""2000 A diameter (i.e. greater than colloidal dimensions), the particles comprising aggregates of crystallites.
Colloidal dispersions prepared from dispersible cerium compounds prepared in accordance with the present invention show, for example, a 10 to 20-fold reduction in this size in that such dispersions include colloidal size particles comprising individual crystallites (N50 ) and small aggregates of crystallites of say ""'100 .
Thus, the heating in the presence of a deaggregating agent in accordance with the present invention achieves deaggregation of the crystallites to enable particles of colloidal dimensions to be obtained.
Deaggregation in accordance with the present invention can involve breaking of bonds between crystallites in an aggregate of crystallites or a weakening of bonds or attractive forces between crystallites in an aggregate of crystallites to a degree that the crystallites can separate when the dispersible cerium compound is introduced into an aqueous medium.
Whilst it is by no means fuily established, it is believed that the heating with acid species in accordance with present invention may involve reaction of acid with hydroxide groups (or oxobridges) which link crystallites together thereby to break down aggregates of crystallites.
Thus, in one embodiment it is believed that nitric acid (formed from water and nitrate ions in the oxide hydrate and supplemented by nitric acid additions if necessary) react with the hydroxide groups (or oxo-bridges) to deaggregate the aggregated crystallites.
The present invention also provides a process for the preparation of a colloidal dispersion of a cerium compound which comprises dispersing in an aqueous medium a dry dispersible cerium compound prepared in accordance with the present invention.
The invention further provides a process for the preparation of a gel which comprises drying a sol which has been prepared by dispersing in an aqueous medium a dry dispersible cerium compound prepared in accordance with the present invention.
The aqueous medium in which the cerium compound is dispersed can be water or aqueous acid solutions (e.g. dilute solutions of nitric acid).
Gels may be produced by evaporating the sols at room temperature (--230C) or at elevated temperature (N500C). The gels are glassy and may be redispersed in water.
The invention further provides a process which comprises mixing a dispersible cerium compound prepared in accordance with the present invention with water at such a concentration that the dispersible cerium compound coagulates to form a slurry and separating the coagulated cerium compound from liquor of the slurry.
The separated coagulated cerium compound may be dispersed in water to form a colloidal dispersion.
By forming a slurry and removing the liquor of the slurry, it is possible to remove anions in the liquor and thereby leave a reduced anion concentration in the coagulated cerium compound. In this way the concentration of anions which may interfere with the formation of a colloidal dispersion is reduced and a more concentrated colloidal dispersion can be formed on admixing the separated coagulated cerium compound with water.
It will be appreciated that where a dispersible cerium compound prepared by heating in accordance with the present invention does not have an anion concentration which prevents a desired concentration of sol being formed, there is no necessity for carrying out the further steps of coagulation to form a slurry, separation and dispersion to reduce the anion concentration.
According to another aspect the present invention provides a sol prepared by a process in accordance with the present invention.
According to a further aspect the present invention provides a gel prepared by a process in accordance with the present invention.
According to yet a further aspect the present invention provides a dry dispersible cerium compound prepared by a process in accordance with the invention.
The invention will now be described, by way of example only, as follows:- Example 1
1 Kg of cerium (IV) oxide hydrate ("Ceria
Hydrate" obtained from Rh6ne Poulenc) was
placed in a saggar and heated for 1 hour in a
muffle furnace at 3200C in air.
The resulting dry dispersible cerium compound
powder (0.78 Kg) had a crystallite size of 59 A and the NONCE (IV) ratio was 0.14.
The degree of aggregation of crystallites in the
"Ceria Hydrate" starting material was much
greater than the degree of aggregation of
crystallites in the dispersible cerium compound.
The "Ceria Hydrate" starting material had a NO-3/CeO2 ratio of 0.1 8.
Example 2
1009 of the dispersible cerium compound
powder prepared in Example 1 was dispersed by stirring in hot dimineralised water to form a sol having a concentration of 645 gl-' CeO2 equivalent.
The dispersible cerium compound was 92.1 w/o dispersible in the hot dimineralised water.
Example 3
1 Og of the dispersible cerium compound
powder prepared in Example 1 was dispersed in
100 cm3 of dimineralised water to form a sol
having a pH of 3.15 and a conductivity of 2.44
mmho.cm-'. After boiling the sol had a conductivity of 3.07 mmho.cm-'.
Example 4
The procedure of Example 1 was followed with the exception that the temperature of heating was 3000 C.
The resulting dry dispersible cerium compound
powder had a NO3/CeO2 ratio of 0.11 and a
crystallite size of 58 A and was dispersible in water to form a sol.
Example 5
The procedure of Example 1 was followed with the exception that the temperature of heating was
3500C.
The resulting dry dispersible cerium compound
powder had a NOVCeO2 ratio of 0.04, a
crystallite size of 60 A and was 80% dispersible in water to form a sol.
Example 6
The procedure o fExample 1 was followed with the exception that the temperature of heating was 4000C.
The resulting dry dispersible cerium cerium compound powder had a NOCeO2 ratio of
0.015, a crystallite size of 65 A and was dispersible to form a sol in water to which a small
amount of HNO3 had been added to give a NO3/CeO2 ratio of 0.09.
Example 7
A washed cerium (IV) hydrate was prepared from Cerium (III) nitrate solution by oxidising with
NH4 OH/H2 2 as disclosed in British Patent
Application No. 22835/78 hereinbefore mentioned.
The cerium (IV) hydrate thus produced was triturated with diluted nitric acid to give a NO=3/CeO2 ratio of 0.23 and then dried at 1 050C to give a substantially dry cerium (IV) oxide hydrate having the composition CeO2 89.1%, NO3 7.4%, H2O (by difference) 3.5%, NOCeO2=0.23).
The substantially dry cerium (IV) oxide hydrate was heated in a furnace at 3200C for 2 hours to give a dry dispersible cerium compound having
CeO2 content of 96.1% and a nitrate content of 2.8% (NO3/CeO2=0.08).
This cerium compound was readily dispersible in water (to 98.9%) to give a stable colloidal dispersion of 400 91- concentration.
Example 8
A 95% pure commercially available cerium (IV) oxide hydrate (containing ~53% oxide and 5 W/o other Rare Earth compounds), which proved to be unsusceptible to deaggregation treatment to produce a colloidal dispersion when treated with aqueous nitric acid at up to NOoxide=0.5 in accordance with British Patent Application No.
22835/78, was treated in accordance with the present invention.
Thus 2509 of the commercially available cerium (IV) hydrate (132.59 oxide) was treated with 1 4.2 cm3 of 1 6M nitric acid and dried at 1 050C to give a substantially dry powder of cerium (IV) oxide hydrate containing 91.0% oxide, 6.9% NQ (NO3/oxide=0.21).
This dry cerium (IV) oxide hydrate was heated in a furnace at 3200C for 1 hour to give a dry dispersible cerium compound containing 94.1% oxide and 5.1% NQ (Nt3/oxide=0.15).
This cerium compound was dispersible in water to give a colloidal dispersion of 100 91-' concentration.
Example 9
Dry dispersible cerium compound prepared as in Example 8 was added to water at a concentration sufficient to effect coagulation on boiling to form a slurry.
The coagulated cerium compound was separated from the "nitrate rich" liquor of the slurry by centrifuging and dispersed by stirring in water to form a colloidal dispersion of 200 gl-1 concentration.
Example 10 50g of 99.5% pure cerium (IV) oxide hydrate (containing 87.6 w/o oxide, and some nitrate anion, as supplied by the manufacturer) were mixed with 20ml of 5.2M hydrochloric acid (chloride CeO2 mole ratio=0.4).
The resulting mixture was dried and heated at 3200C for 30 minutes.
The resulting dry dispersible cerium compound powder was readily dispersible in water to give a stable sol of at least 200 gl-1 concentration. This sol had a pH of 1.2 and a conductivity of 29.6 mmhos.
Example 11 50g of a 99.5% pure cerium (IV) oxide hydrate (containing 93.0 woo oxide and containing no nitrate anions as supplied by the manufacturers) were mixed with 21 ml of 5.3M hydrochloric acid (chloride/CeO2 mole ratio 0.4).
The resulting mixture was dried and heated at 3200C for 35 minutes to give a dry dispersible cerium compound powder.
Example 12
lOg of dry dispersible cerium compound powder prepared as in Example 11 were added to 25m1 of hot water to form a dilute dispersion which on heating coagulated to form a clear supernatent liquor and a precipitate.
After centrifuging, the supernatant liquor was discarded and the residue dispersed in water to form a stable sol containing 200 gr1 of oxide.
The sol had a pH of 1.3 and a conductivity of 20.8 mmhos.
Example 13 50g of 99.5% pure cerium (IV) oxide hydrate (containing 87.6 w/o oxide and some nitrate anion) were mixed with 20ml of 6.OM perchloric acid (ClO,/CeO2 mole rntio,=0.4).
The resulting mixture was dried and heated at 3200C for 30 minutes to give a dry dispersible cerium compound powder.
Example 14
The dry dispersible cerium compound powder prepared in Example 14 was readily dispersed in water to give a stable sol containing at least 200 gr1 of cerium oxide with a pH of 1.8 and a conductivity of 8.8 mmhos.
Claims (22)
1. A process for the preparation of a dispersible cerium compound which comprises heating a substantially dry cerium (IV) oxide hydrate in the presence of a deaggregating agent to cause deaggregation of aggregated crystallites in the cerium (IV) oxide hydrate and produce a dry dispersible cerium compound.
2. A process as claimed in claim 1 wherein the deaggregating agent comprises acid species.
3. A process as claimed in claim 2 wherein the acid species include nitrate anions, chloride anions, prechlorate anions, or any combination thereof.
4. A process as claimed in claim 2 or 3 wherein prior to heating acid species are introduced to the cerium (IV) oxide hydrate.
5. A process as claimed in any one of claims 2 to 4 wherein the acid species include nitrate anions and the nitrate/CeO2 ratio in the cerium (IV) oxide hydrate is in the range 0.15 to 0.35.
6. A process as claimed in any one of the preceding claims wherein the cerium (IV) oxide hydrate is heated to a temperature in the range 200-4500C.
7. A process as claimed in claim 6 wherein the cerium (IV) oxide hydrate is heated to a temperature in the range 300-3500C.
8. A process as claimed in any one of the preceding claims further comprising the step of dispersing the dry dispersible cerium compound in an aqueous medium to give a colloidal dispersion of a cerium compound.
9. A process as claimed in claim 8 wherein the aqueous medium is water or an aqueous acid solution.
10. A process as claimed in any one of claims 1 to 7 further comprising the steps of mixing the dispersible cerium compound with water at such a concentration that the dispersible cerium compound coagulates to form a slurry and separating the coagulated cerium compound from liquor of the slurry.
11. A process as claimed in claim 10 wherein the separated coagulated cerium compound is dispersed in water to form a colloidal dispersion.
1 2. A process for the preparation of a gel which comprises drying a sol which has been prepared by dispersing in an aqueous medium a dry dispersible cerium compound prepared by a process as claimed in any one of claims 1 to 7.
13. A process for the preparation of a gel which comprises drying a sol which has been prepared by a process as claimed in any one of claims 8, 9 and 11.
1 4. A dry dispersible cerium compound prepared by a process as claimed in any one of claims 1 to 7.
1 5. A dry dispersible cerium compound as claimed in claim 14 wherein nitrate anions are present and the nitrate/CeO2 ratio is in the range 0.05 to 0.25.
16. A dry dispersible cerium compound as claimed in claim 1 5 wherein the nitrate/CeO2 ratio is in the range 0.08-0.1 5.
1 7. A sol prepared by a process as claimed in any one of claims 8,9 and 11.
18. A gel prepared by a process as claimed in claim 12 or claim 13.
1 9. A process for the preparation of a dry dispersible cerium compound substantially as hereinbefore described with reference to any one of Examples 1,4,5,6,7,8,10,11 and 13.
20. A dry dispersible cerium compound substantially as hereinbefore described with reference to any one of Examples 1,4, 5, 6, 7, 8, 10,11 and 13.
21. A process for the preparation of a colloidal dispersion substantially as hereinbefore described with reference to any one of Examples 2, 3, 6, 7, 8,9,10,12 and 14.
22. A colloidal dispersion substantially as hereinbefore described with reference to any one of Examples2,3,6,7,8,9,10,12 10,12 and 14.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8112046A GB2075478B (en) | 1980-05-09 | 1981-04-16 | Improvements in or relating to cerium compounds |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8015395 | 1980-05-09 | ||
GB8112046A GB2075478B (en) | 1980-05-09 | 1981-04-16 | Improvements in or relating to cerium compounds |
Publications (2)
Publication Number | Publication Date |
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GB2075478A true GB2075478A (en) | 1981-11-18 |
GB2075478B GB2075478B (en) | 1983-10-12 |
Family
ID=26275455
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8112046A Expired GB2075478B (en) | 1980-05-09 | 1981-04-16 | Improvements in or relating to cerium compounds |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0078098A2 (en) * | 1981-08-07 | 1983-05-04 | United Kingdom Atomic Energy Authority | Cerium compounds |
FR2583736A1 (en) * | 1985-06-20 | 1986-12-26 | Rhone Poulenc Spec Chim | NEW CERIUM IV COMPOUND AND PROCESS FOR PREPARING THE SAME |
EP0239479A2 (en) * | 1986-03-26 | 1987-09-30 | Rhone-Poulenc Chimie | Aqueous colloidal dispersions of a cerium IV compound, and process for their preparation |
EP0239477A2 (en) * | 1986-03-26 | 1987-09-30 | Rhone-Poulenc Chimie | Cerium IV compound and process for its preparation |
FR2716388A1 (en) * | 1994-02-18 | 1995-08-25 | Rhone Poulenc Chimie | New cerium di:oxide organosol |
EP0671205A2 (en) * | 1994-02-18 | 1995-09-13 | Rhone-Poulenc Chimie | Organic sole of or tetravalent metal oxid and their use as additive in hydrocarbon compositions |
EP0947469A2 (en) * | 1996-07-30 | 1999-10-06 | Nissan Chemical Industries, Limited | Abrasive |
US6136048A (en) * | 1995-11-22 | 2000-10-24 | Rhodia Chimie | Organic sol comprising at least one oxygenated rare-earth compound, synthesis method therefor, and use of said sol for catalysis |
US6210451B1 (en) | 1995-02-21 | 2001-04-03 | Rhone-Poulenc Chimie | Colloidal organic sols comprising tetravalent metal oxide/organic acid complexes |
-
1981
- 1981-04-16 GB GB8112046A patent/GB2075478B/en not_active Expired
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0078098A2 (en) * | 1981-08-07 | 1983-05-04 | United Kingdom Atomic Energy Authority | Cerium compounds |
EP0078098A3 (en) * | 1981-08-07 | 1983-07-27 | United Kingdom Atomic Energy Authority | Cerium compounds |
FR2583736A1 (en) * | 1985-06-20 | 1986-12-26 | Rhone Poulenc Spec Chim | NEW CERIUM IV COMPOUND AND PROCESS FOR PREPARING THE SAME |
EP0208580A1 (en) * | 1985-06-20 | 1987-01-14 | Rhone-Poulenc Chimie | Cerium IV compound and method for its preparation |
US5344588A (en) * | 1985-06-20 | 1994-09-06 | Rhone-Poulenc Specialites Chimiques | Cerium (IV) compound |
US5035834A (en) * | 1986-03-26 | 1991-07-30 | Rhone-Poulenc Chimie | Novel cerium (IV) compounds |
FR2596382A1 (en) * | 1986-03-26 | 1987-10-02 | Rhone Poulenc Chimie | AQUEOUS COLLOIDAL DISPERSIONS OF A CERIUM IV COMPOUND AND PROCESS FOR OBTAINING THEM |
EP0239477A3 (en) * | 1986-03-26 | 1987-11-25 | Rhone-Poulenc Chimie | Cerium iv compound and process for its preparation |
EP0239479A3 (en) * | 1986-03-26 | 1987-12-09 | Rhone-Poulenc Chimie | Aqueous colloidal dispersions of a cerium iv compound, and process for their preparation |
US5021192A (en) * | 1986-03-26 | 1991-06-04 | Rhone-Poulenc Chimie | Colloidal dispersions of cerium (IV) compound |
EP0239477A2 (en) * | 1986-03-26 | 1987-09-30 | Rhone-Poulenc Chimie | Cerium IV compound and process for its preparation |
EP0239479A2 (en) * | 1986-03-26 | 1987-09-30 | Rhone-Poulenc Chimie | Aqueous colloidal dispersions of a cerium IV compound, and process for their preparation |
FR2716388A1 (en) * | 1994-02-18 | 1995-08-25 | Rhone Poulenc Chimie | New cerium di:oxide organosol |
EP0671205A2 (en) * | 1994-02-18 | 1995-09-13 | Rhone-Poulenc Chimie | Organic sole of or tetravalent metal oxid and their use as additive in hydrocarbon compositions |
EP0671205A3 (en) * | 1994-02-18 | 1995-09-20 | Rhone-Poulenc Chimie | Organic sole of or tetravalent metal oxid and their use as additive in hydrocarbon compositions |
US6210451B1 (en) | 1995-02-21 | 2001-04-03 | Rhone-Poulenc Chimie | Colloidal organic sols comprising tetravalent metal oxide/organic acid complexes |
US6136048A (en) * | 1995-11-22 | 2000-10-24 | Rhodia Chimie | Organic sol comprising at least one oxygenated rare-earth compound, synthesis method therefor, and use of said sol for catalysis |
EP0947469A2 (en) * | 1996-07-30 | 1999-10-06 | Nissan Chemical Industries, Limited | Abrasive |
EP0947469A3 (en) * | 1996-07-30 | 2000-01-12 | Nissan Chemical Industries, Limited | Abrasive |
US6372003B1 (en) | 1996-07-30 | 2002-04-16 | Nissan Chemical Industries, Ltd. | Polishing abrasive of crystalline ceric oxide particles having surfaces modified with hydroxyl groups |
Also Published As
Publication number | Publication date |
---|---|
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
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PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930416 |