EP0690749A1 - Zirconium silicate grinding medium and method of milling - Google Patents
Zirconium silicate grinding medium and method of millingInfo
- Publication number
- EP0690749A1 EP0690749A1 EP95908662A EP95908662A EP0690749A1 EP 0690749 A1 EP0690749 A1 EP 0690749A1 EP 95908662 A EP95908662 A EP 95908662A EP 95908662 A EP95908662 A EP 95908662A EP 0690749 A1 EP0690749 A1 EP 0690749A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- powder
- range
- zirconium silicate
- particle size
- milling
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/18—Details
- B02C17/20—Disintegrating members
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/18—Adding fluid, other than for crushing or disintegrating by fluid energy
Definitions
- the invention relates to grinding media and more particularly to zirconium silicate grinding media.
- milling devices such as disc mills, cage mills, and/or attrition mills are used with a milling medium to produce such finely divided powders, ideally to reduce the powder to its ultimate state of division such as, for example, to the size of a single powder crystallite.
- Milling of some powders involves a de-agglomeration process according to which chemical bonds, such as hydrogen-bonded surface moisture, Van der Waals and electrostatic forces, such as between particles, as well as any other bonds which are. keeping the particles together, must be broken and/or overcome in order to obtain particles in their state of ultimate division.
- One pigment powder which entails a de-agglomeration milling process to reduce it to a finely divided powder is titanium dioxide.
- Optimal dispersal of titanium dioxide pigment powder results in optimized performance properties, particularly improved gloss, durability and hiding power.
- De-agglomeration processes are best performed using a grinding medium characterized by a small particle size which is the smallest multiple of the actual size of the product particles being milled which can still be effectively separated from the product powder.
- the grinding medium can be separated from the product particles using density separation techniques.
- separation of the grinding medium from the product can be effected on the basis of differences between settling rate, particle size or both parameters existing between the grinding medium and product powder particles.
- Commercial milling applications typically use silica sand, glass beads, ceramic media or steel balls, for example, as grinding media.
- the low density of about 2.6g/cc, of sand and glass beads and the low hardness of glass beads restricts the materials which can be milled using sand or glass beads.
- the use of steel shot is restricted only to those applications where iron contamination resulting from wear products of the steel shot during the milling process can be tolerated.
- the invention provides a relatively inexpensive, dense and non-toxic, naturally occurring zirconium silicate sand grinding medium which has small particle size and a sufficiently high density to make it suitable for grinding a wide range of materials, while not contaminating the product powder with its wear byproducts as well as a method for milling a powder using this grinding medium.
- a naturally occurring zirconium silicate sand characterized by a density in the range of from about 4g/cc absolute to about 6g/cc absolute, more preferably in the range of from about 4.6g/cc absolute to about 4.9g/cc absolute and most preferably in the range of from about 4.75g/cc absolute to about 4.85g/cc absolute is provided.
- Another aspect of the invention provides a method for milling a powder comprising steps of providing a starting powder characterized by a starting powder particle size and a naturally occurring zirconium silicate sand grinding medium characterized by a grinding medium density in the range of from about 4.Og/cc absolute to about 6.Og/cc absolute and mixing the starting powder and the grinding medium with a liquid medium to form a milling slurry; milling the milling slurry for a time sufficient to produce a product slurry including a product powder having a desired product powder particle size and having substantially the same composition as the starting powder and separating the product slurry from the milling slurry.
- An object of this invention is to provide a naturally occurring zirconium silicate sand grinding medium.
- Another object of this invention is to provide a method for milling a powder using a naturally occurring zirconium silicate sand grinding medium.
- the term "naturally occurring" indicates that the zirconium silicate sand is mined in the form of zirconium silicate sand of a particular particle size and is distinguished from zirconium silicate materials which are synthesized, manufactured or otherwise artificially produced by man.
- the zirconium silicate sand grinding medium of the invention occurs in nature in the appropriate size and shape which can be sorted to obtain the appropriate fraction for use in a particular grinding operation.
- the mined zirconium silicate sand is sorted to isolate the appropriate fraction of zirconium silicate sand, based on particle size considerations, to be used as a grinding medium.
- grinding medium refers to a material which is placed in a milling device, such as a disc mill, cage mill or attrition mill, along with the powder to be ground more finely or de-agglomerated to transmit shearing action of the milling device to the powder being processed to break apart particles of the powder.
- the invention provides a grinding medium including naturally occurring zirconium silicate sand characterized by a density in the range of from about 4g/cc to about 6g/cc, more preferably in the range of from about 4.6g/cc to about 4.9g/cc and most preferably in the range of from about 4.75g/cc to about 4.85g/cc.
- the naturally occurring zirconium silicate sand tends to be single phase, while synthetic zirconium silicate ceramic beads are typically multiphase materials.
- Surface contaminants such as aluminum, iron, uranium, thorium and other heavy metals as well as Ti0 2 can be present on the surfaces of the naturally occurring zirconium silicate sand particles. Once the surface contaminants are removed by any surface preconditioning process known to one skilled in the art, such as, for example, washing and classifying, chemical analyses indicate that any remaining contaminants are within the crystal structure of the zirconium silicate and do not adversely affect the powder being milled.
- the zirconium silicate sand grinding medium can be characterized by a particle size which is the smallest multiple of the particle size of the finished product particle size, the milled product powder particle size, which can be effectively separated from the milled product powder.
- the naturally occurring zirconium silicate sand particle size is greater than lOOmicron ⁇ and can be in the range of from about lOOmicrons to about 1500microns, more preferably in the range of from about lOOmicrons to about 500microns and most preferably in the range of from about 5150microns to about 250microns.
- the mined, naturally occurring zirconium silicate sand can be screened using techniques well known to one skilled in the art to isolate a coarse fraction of sand having particles of an appropriate size to function as an effective grinding medium.
- the grinding medium can be any liquid medium compatible with the product being milled and the milling process and can include water, oil, any other organic compound or a mixture thereof, and can be combined with the naturally occurring zirconium silicate sand to form a slurry.
- the liquid medium 5 is selected depending upon the product being milled.
- the milled product powder may or may not be separated from the liquid medium after the milling process is complete; however, the grinding medium is usually separated from the liquid medium after the milling process is complete.
- the liquid medium can be an oil such as a naturally derived oil like tung oil, linseed oil, soybean oil or tall oil or mixtures thereof. These naturally occurring oils can be mixed with solvents such as mineral spirits, 5naphtha or toluol or mixtures thereof which can further include substances such as gums, resins, dispersants and/or drying agents.
- the liquid medium can also include other materials used in the manufacture of oil based paints and inks such as alkyd resins, epoxy resins, nitrocellulose, melamines, 0urethanes and silicones.
- the liquid medium can be water, optionally including antifoaming agents and/or dispersants.
- the powder is a ceramic or magnetic powder
- the medium can be water and can also include dispersants. 5
- the naturally occurring zirconium silicate sand and the liquid medium can be combined to form a grinding slurry which is further characterized by a grinding slurry viscosity which can be in the range of from about l.Ocps to about 10,000cps, more preferably in the range of from about l.Ocps to about
- the grinding slurry viscosity is determined by the concentration of solids in the grinding slurry and, thus, the higher the concentration of solids in the grinding slurry, the higher will be the grinding slurry
- the invention also provides a method for milling a powder including steps of providing a starting powder characterized by a starting powder particle size; providing a grinding medium including naturally occurring zirconium silicate sand characterized by a grinding medium density in the range of
- the starting powder used in the method of the invention can be an agglomerated and/or aggregated powder.
- the agglomerated powder can be characterized by an agglomerated powder particle size less than about 500microns and more preferably can be in the range of from about O.Olmicron to about 200microns.
- the agglomerated powder has a particle size of in the range of from about 0.05micron to about lOOmicrons which can be milled to approach the particle size of an individual titanium dioxide crystallite.
- the starting powder can also be characterized by a starting powder density in the range of from about 0.8g/cc absolute to about 5.Og/cc absolute.
- the method of the invention is suitable for organic powders which typically have densities on the lower end of the above range as well as for inorganic powders such as titanium dioxide, calcium carbonate, bentonite or kaolin or mixtures thereof.
- the titanium dioxide starting powder can be an agglomerated titanium dioxide pigment which has a density in the range of from about 3.7g/cc to about 4.2g/cc.
- the naturally occurring zirconium silicate sand used in the method of the invention can also be characterized by a zirconium silicate sand particle size greater than about lOOmicrons and can be in the range of from about lOOmicrons to about 1500microns, more preferably in the range of from about lOOmicrons to about 500microns and most preferably in the range of from about 150microns to about 250microns.
- the liquid medium used in the method of the invention can be oil or water selected according to the criteria already described.
- Step (5) of milling can be carried out in any suitable milling device which employs a grinding medium, such as, but not limited to, a bead mill, cage mill, disc mill or pin mill designed to support a vertical flow or horizontal flow.
- a grinding medium such as, but not limited to, a bead mill, cage mill, disc mill or pin mill designed to support a vertical flow or horizontal flow.
- the milling process can be a batch or continuous process.
- Step (6) of separating the product slurry from the milling slurry can be accomplished by distinguishing the product slurry, which contains the product powder along with liquid medium from the milling slurry on the basis of a difference between starting powder and grinding medium physical properties and product powder particle physical properties such as particle size, particle density and particle settling rate.
- the product powder may or may not be separated from the liquid medium after the milling process is complete; however, the grinding medium is usually separated from the liquid medium after the milling process is complete.
- the product powder can be separated from the product slurry and subjected to further processing such as dispersing the powder in a dispersing medium to form a dispersion.
- the dispersing medium can be selected according to the same criteria as already described for the selection of the liquid medium. If the product powder is to be used in the product slurry, no further dispersing steps are needed.
- the following examples are provided. The particular compounds, processes and conditions utilized in the examples are meant to be illustrative of the present invention and are not limited thereto.
- Sand mills having nominal grinding chamber capacities of 275 gallons and overall capacities of 500 gallons were loaded separately with 3000 pounds of synthetic zirconium silicate ceramic beads of nominal 300micron and 210micron size and with
- the feed slurries fed through all mills had a density of 1.35g/cc and contained titanium dioxide, approximately 40% of which was less than 0.5micron in size in water.
- the size of the titanium dioxide particles in the product slurry was measured using a Leeds and Northrupp
- Example 2 is provided to compare the performance of synthetic zirconium silicate ceramic beads with the performance of the naturally occurring zirconium silicate sand
- the naturally occurring zirconium silicate sand has a higher density than the 3.8g/cc density of synthetic zirconium silicate products which allows use of smaller naturally occurring zirconium silicate sand particles by comparison with
- 15naturally occurring zirconium silicate sand can be used successfully at production flowrates to effect removal of coarse particles, having a particle size greater than 0.5micron in a titanium dioxide pigment. No appreciable loss of media from the mill was observed.
- Example 2 was conducted by changing flowrates in mill B, operating with conventional silica sand, and of mill C, operating with naturally occurring zirconium silicate sand.
- Sand loadings in mill B and mill C were similar to those used in Example 1, i.e., 1200 pounds of silica sand in mill B and
- Contamination of the pigment product from the naturally occurring zirconium silicate sand grinding medium was minimal as measured by x-ray fluorescence examination of the pigment solids found in the mill overflow. Metal contaminant levels also measured by x-ray fluorescence were similar to those observed in pigments milled using a conventional silica sand grinding medium.
- the optical quality of the pigment milled with the naturally occurring zirconium silicate sand as measured by the B381 dry color and brightness test which is defined as the total light reflected from a powder compact surface and the spectrum of reflected light i.e. color, was comparable to that obtained for samples milled using conventional silica sand. Results of these tests are summarized in Table 3.
- mill C was inspected for signs of wear on the rubber lining using a fiber optic probe inserted through a flange in the underside of the mill. Essentially no signs of wear on the rubber lining were observed as indicated by the condition of the weavelike pattern on the rubber mill lining which is normally present on the surface of freshly lined mills.
- the mill lining showed considerable wear, especially to the leading edges of the mill rotor bars where the weavelike pattern had been almost completely worn away.
- Example 3 The following example is provided to show the differences in particle size, impurity content and grinding performance among naturally occurring zirconium silicate sands obtained from different natural sources.
- Sample 1 Three naturally occurring zirconium silicate sand samples, hereinafter referred to as Sample 1, Sample 2 and Sample 3 were evaluated for particle size using a screen analysis conducted for thirty minutes on a RotapTM. Based on the data presented in Table 4, Sample 2 and Sample 3 are similar with respect to particle size, while Sample 1 is smaller, which can make it difficult to retain Sample 1 sand in a cage mill during a continuous process.
- a laboratory scale grinding study was also performed with the three naturally occurring zirconium silicate sands. The study was conducted in a cage mill under a standard laboratory sand load of 1.8:1 zirconium sand to pigment load. Table 6 shows the percent of particles passing 0.5micron, i.e., particles having sizes smaller than O.Smicron, after 2, 4 and 8 minutes of grinding, as well as the median particle diameter at these times.
- the pigment was an untreated interior enamel grade titanium dioxide pigment. Particle sizes were determined using a MicrotracTM particle size analyzer as has been described before.
Landscapes
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Crushing And Grinding (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Disintegrating Or Milling (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Silicon Compounds (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99103983A EP0930098B1 (en) | 1994-01-25 | 1995-01-24 | Zirconium silicate grinding medium |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18608594A | 1994-01-25 | 1994-01-25 | |
US186085 | 1994-01-25 | ||
PCT/US1995/000963 WO1995019846A1 (en) | 1994-01-25 | 1995-01-24 | Zirconium silicate grinding medium and method of milling |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99103983A Division EP0930098B1 (en) | 1994-01-25 | 1995-01-24 | Zirconium silicate grinding medium |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0690749A1 true EP0690749A1 (en) | 1996-01-10 |
EP0690749A4 EP0690749A4 (en) | 1996-10-30 |
EP0690749B1 EP0690749B1 (en) | 2000-03-29 |
Family
ID=22683601
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95908662A Expired - Lifetime EP0690749B1 (en) | 1994-01-25 | 1995-01-24 | Method of milling with a zirconium silicate grinding medium |
EP99103983A Expired - Lifetime EP0930098B1 (en) | 1994-01-25 | 1995-01-24 | Zirconium silicate grinding medium |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99103983A Expired - Lifetime EP0930098B1 (en) | 1994-01-25 | 1995-01-24 | Zirconium silicate grinding medium |
Country Status (18)
Country | Link |
---|---|
EP (2) | EP0690749B1 (en) |
JP (1) | JP2693039B2 (en) |
KR (1) | KR0164652B1 (en) |
CN (1) | CN1042104C (en) |
AT (2) | ATE235318T1 (en) |
AU (1) | AU671248B2 (en) |
BR (1) | BR9506238A (en) |
CA (1) | CA2158969C (en) |
CZ (1) | CZ284563B6 (en) |
DE (2) | DE69530132T2 (en) |
ES (2) | ES2190624T3 (en) |
FI (1) | FI954466A (en) |
MX (1) | MX9504066A (en) |
PL (1) | PL176837B1 (en) |
SK (1) | SK117895A3 (en) |
TW (1) | TW276208B (en) |
WO (1) | WO1995019846A1 (en) |
ZA (1) | ZA95590B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2315505B (en) * | 1996-07-24 | 1998-07-22 | Sofitech Nv | An additive for increasing the density of a fluid and fluid comprising such additve |
DE102004040368B3 (en) * | 2004-08-20 | 2006-02-23 | Juhnke, Michael, Dipl.-Ing. | Grinding body for producing very finely ground product has surface consisting of material which is rigid at grinding temperature but not at room temperature |
US20080022900A1 (en) * | 2006-07-25 | 2008-01-31 | Venkata Rama Rao Goparaju | Process for manufacturing titanium dioxide pigment |
CN101722085B (en) * | 2008-10-15 | 2012-06-13 | 许兴康 | Grinding technology of high purity sub-nano level superfine zirconium silicate powder |
CN102795848B (en) * | 2012-08-02 | 2013-10-23 | 江苏锡阳研磨科技有限公司 | Low-temperature sintered zirconium silicate grinding ball and preparation method thereof |
CN111180719A (en) * | 2020-01-07 | 2020-05-19 | 马鞍山科达普锐能源科技有限公司 | Method for preparing nano silicon by three-stage grinding |
CN115043620B (en) * | 2022-03-09 | 2023-03-10 | 湖北工业大学 | Method for preparing early-strength precast concrete by taking sand as grinding medium |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60211637A (en) * | 1984-04-05 | 1985-10-24 | Hitachi Maxell Ltd | Production of magnetic recording medium |
EP0483808A1 (en) * | 1990-10-31 | 1992-05-06 | Matsushita Electric Industrial Co., Ltd. | Agitating mill and method for milling |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB679552A (en) * | 1949-08-29 | 1952-09-17 | British Titan Products | Improvements relating to methods and apparatus for grinding, crushing and disintegrating |
US3337140A (en) * | 1964-06-03 | 1967-08-22 | Pittsburgh Plate Glass Co | Dispersion process |
DE2832761B1 (en) * | 1978-07-26 | 1979-10-31 | Basf Ag | Process for converting crude and / or coarsely crystallized perylene tetracarboxylic diimides into a pigment form |
JPS5815079A (en) * | 1981-07-14 | 1983-01-28 | 日本化学陶業株式会社 | Crusher member comprising zirconia sintered body |
US4547534A (en) * | 1983-03-18 | 1985-10-15 | Memorex Corporation | Method to disperse fine solids without size reduction |
-
1995
- 1995-01-24 BR BR9506238A patent/BR9506238A/en not_active IP Right Cessation
- 1995-01-24 ES ES99103983T patent/ES2190624T3/en not_active Expired - Lifetime
- 1995-01-24 CN CN95190048A patent/CN1042104C/en not_active Expired - Lifetime
- 1995-01-24 DE DE69530132T patent/DE69530132T2/en not_active Expired - Fee Related
- 1995-01-24 ES ES95908662T patent/ES2143616T3/en not_active Expired - Lifetime
- 1995-01-24 AT AT99103983T patent/ATE235318T1/en not_active IP Right Cessation
- 1995-01-24 EP EP95908662A patent/EP0690749B1/en not_active Expired - Lifetime
- 1995-01-24 KR KR1019950704087A patent/KR0164652B1/en not_active IP Right Cessation
- 1995-01-24 SK SK1178-95A patent/SK117895A3/en unknown
- 1995-01-24 DE DE69515935T patent/DE69515935T2/en not_active Expired - Fee Related
- 1995-01-24 AT AT95908662T patent/ATE191160T1/en not_active IP Right Cessation
- 1995-01-24 PL PL95310446A patent/PL176837B1/en not_active IP Right Cessation
- 1995-01-24 EP EP99103983A patent/EP0930098B1/en not_active Expired - Lifetime
- 1995-01-24 AU AU16900/95A patent/AU671248B2/en not_active Ceased
- 1995-01-24 MX MX9504066A patent/MX9504066A/en not_active IP Right Cessation
- 1995-01-24 CZ CZ952357A patent/CZ284563B6/en not_active IP Right Cessation
- 1995-01-24 WO PCT/US1995/000963 patent/WO1995019846A1/en active IP Right Grant
- 1995-01-24 JP JP7519738A patent/JP2693039B2/en not_active Expired - Fee Related
- 1995-01-24 CA CA002158969A patent/CA2158969C/en not_active Expired - Fee Related
- 1995-01-25 ZA ZA95590A patent/ZA95590B/en unknown
- 1995-03-01 TW TW084101912A patent/TW276208B/zh active
- 1995-09-21 FI FI954466A patent/FI954466A/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60211637A (en) * | 1984-04-05 | 1985-10-24 | Hitachi Maxell Ltd | Production of magnetic recording medium |
EP0483808A1 (en) * | 1990-10-31 | 1992-05-06 | Matsushita Electric Industrial Co., Ltd. | Agitating mill and method for milling |
Non-Patent Citations (4)
Title |
---|
DATABASE WPI Section PQ, Week 8310 Derwent Publications Ltd., London, GB; Class P41, AN 83-23662k XP002012464 & JP-A-58 015 079 (NIPPON KAGAKU TOGYO) , 28 January 1983 * |
KIRK-OTHMER 'Encyclopedia of Chemical Technology', 1984, JOHN WILEY AND SONS, VOL. 24, PAGES 864 - 865, NEW YORK * |
PATENT ABSTRACTS OF JAPAN vol. 010, no. 074 (P-439), 25 March 1986 & JP-A-60 211637 (HITACHI MAXELL KK), 24 October 1985, * |
See also references of WO9519846A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2158969A1 (en) | 1995-07-27 |
EP0690749B1 (en) | 2000-03-29 |
DE69515935T2 (en) | 2000-08-17 |
CA2158969C (en) | 2000-06-27 |
MX9504066A (en) | 1997-05-31 |
ATE191160T1 (en) | 2000-04-15 |
FI954466A0 (en) | 1995-09-21 |
TW276208B (en) | 1996-05-21 |
AU1690095A (en) | 1995-08-08 |
KR960700819A (en) | 1996-02-24 |
EP0690749A4 (en) | 1996-10-30 |
JP2693039B2 (en) | 1997-12-17 |
EP0930098B1 (en) | 2003-03-26 |
AU671248B2 (en) | 1996-08-15 |
ZA95590B (en) | 1996-07-25 |
CN1042104C (en) | 1999-02-17 |
WO1995019846A1 (en) | 1995-07-27 |
EP0930098A1 (en) | 1999-07-21 |
ES2190624T3 (en) | 2003-08-01 |
CZ235795A3 (en) | 1996-02-14 |
FI954466A (en) | 1995-09-21 |
PL310446A1 (en) | 1995-12-11 |
JPH08506527A (en) | 1996-07-16 |
CN1122112A (en) | 1996-05-08 |
CZ284563B6 (en) | 1999-01-13 |
SK117895A3 (en) | 1996-01-10 |
DE69530132D1 (en) | 2003-04-30 |
DE69515935D1 (en) | 2000-05-04 |
KR0164652B1 (en) | 1998-12-15 |
BR9506238A (en) | 1997-09-30 |
ATE235318T1 (en) | 2003-04-15 |
DE69530132T2 (en) | 2004-01-08 |
ES2143616T3 (en) | 2000-05-16 |
PL176837B1 (en) | 1999-08-31 |
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