CN1701108A - Cerium-based polishing material - Google Patents
Cerium-based polishing material Download PDFInfo
- Publication number
- CN1701108A CN1701108A CNA2004800007749A CN200480000774A CN1701108A CN 1701108 A CN1701108 A CN 1701108A CN A2004800007749 A CNA2004800007749 A CN A2004800007749A CN 200480000774 A CN200480000774 A CN 200480000774A CN 1701108 A CN1701108 A CN 1701108A
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- China
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- weight
- treo
- cerium
- ratio
- rare earth
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Links
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 81
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title abstract description 11
- 238000005498 polishing Methods 0.000 title abstract 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 53
- 239000011737 fluorine Substances 0.000 claims abstract description 39
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 39
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 31
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 22
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 20
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 13
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000003082 abrasive agent Substances 0.000 claims description 62
- 150000002910 rare earth metals Chemical class 0.000 claims description 34
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 18
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 18
- 229910052746 lanthanum Inorganic materials 0.000 claims description 15
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 13
- 238000002441 X-ray diffraction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- 229910017488 Cu K Inorganic materials 0.000 claims description 8
- 229910017541 Cu-K Inorganic materials 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 8
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 5
- 230000005260 alpha ray Effects 0.000 claims description 4
- 239000011521 glass Substances 0.000 abstract description 18
- -1 ranthanum Chemical compound 0.000 abstract description 7
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 description 85
- 239000000126 substance Substances 0.000 description 78
- 230000000052 comparative effect Effects 0.000 description 45
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 35
- 239000002994 raw material Substances 0.000 description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 13
- 239000002002 slurry Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000000638 solvent extraction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000004334 fluoridation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MTRHQJCFFBJGMG-UHFFFAOYSA-N [O-2].[La+3].[F].[O-2].[O-2].[La+3] Chemical group [O-2].[La+3].[F].[O-2].[O-2].[La+3] MTRHQJCFFBJGMG-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910017768 LaF 3 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000021463 dry cake Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- SBNFWQZLDJGRLK-UHFFFAOYSA-N phenothrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 SBNFWQZLDJGRLK-UHFFFAOYSA-N 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
A cerium-based polishing material having rare earth metal oxides as the main component thereof which contains fluorine and at least cerium, ranthanum, praseodymium and neodymium as rare earth elements, wherein the proportion (Nd2O3/TREO) of the weight of neodymium oxide in the total weight (TREO) of rare earth elements in oxide terms is 0.001 to 5 wt %. The use of the above polishing material in the polishing of a face, such as glass, to be polished allows the reduction of the time required for the polishing and also allows more sure inhibition of the occurrence of flaws, as compared to the case of using a conventional cerium based polishing material.
Description
Technical field
The present invention relates to the cerium oxide is the cerium based abrasive material of principal constituent.
Background technology
Cerium based abrasive material can be raw material pulverizing such as fluoro-carbon-cerium ore concentrate, the roasting of the rare earth element of representative by being rich in the cerium for example, carry out classification then as required and make.The cerium based abrasive material that makes is with cerium oxide (CeO
2Deng) be the abrasive substance (for example) of principal constituent with reference to open the flat 1-266183 of communique number of Japan's special permission, also contain the oxide compound of the lanthanum trioxide rare earth elements except that cerium such as (La2O3 etc.) in addition.In addition, the abrasive substance that can obtain higher grinding rate has the cerium based abrasive material (for example, with reference to open communique 2002-097457 number of Japan's special permission) of fluorine-containing (F)
Generally the requirement to abrasive substance is, abrasive power is high as far as possible, and it is smooth as far as possible to grind the resulting abrasive surface in back.Abrasive power is for example embodied by the height of grinding rate.That is, require abrasive substance to have higher grinding rate.In addition, as the abrasive substance that can obtain slick abrasive surface, require it can not cause damage to abrasive surface.
But the cerium based abrasive material in the past that contains fluorine-containing abrasive substance may not have satisfactory performance aspect grinding rate and generation damage.For example, there is the field of making precision instrument, electronics or their component in the field that the demand of cerium based abrasive material is increased, in this field, on the purposes such as surface grinding of component etc., need that grinding rate is higher, damage more is difficult to the abrasive substance that produces.
Summary of the invention
The present invention is exactly the invention of finishing in view of above problem, and purpose is to provide that grinding rate is higher, cerium based abrasive material still less takes place in damage.
Inventor of the present invention has carried out research repeatedly to the grinding rate and the damage generation of cerium based abrasive material, when finding that finally containing ratio with Neodymium trioxide is controlled at the regulation ratio, then the grinding rate of cerium based abrasive material is higher, and damage more is difficult to take place, and has finally finished the present invention thus.
The present invention is to be the cerium based abrasive material of principal constituent with fluorine (F) and rare-earth oxide, contained rare earth element has cerium (Ce), lanthanum (La), praseodymium (Pr), neodymium (Nd) at least in the aforementioned rare-earth oxide, and the weight of Neodymium trioxide accounts for the ratio (Nd of total rare earth (TRE) type oxide converted weight (below, be designated as TREO)
2O
3/ TREO) be 0.001 weight %～5 weight %.The total weight of the weight when TREO is meant and converts each contained in object rare earth element to rare-earth oxide (conversion), can by to the compositional analysis of object material, calculate and try to achieve.When not knowing the situation that the object material is formed, TREO can obtain by following method: as required, to sample dissolve, pre-treatment such as dilution, make the form precipitation of all rare earth elements then with oxalate, then again through filtration, dry, roasting, after forming rare-earth oxide, quality measurement.
For example in the cerium based abrasive material of being put down in writing in patent documentation 1 in the past, it is about 9% that the weight of Neodymium trioxide accounts for the ratio of TREO (below, also be designated as containing ratio sometimes), and in contrast to this, the containing ratio of the Neodymium trioxide in the cerium based abrasive material of the present invention is quite low.The result of research shows, the cerium based abrasive material of the ratio of the weight of Neodymium trioxide in TREO in above-mentioned scope has higher grinding rate, more is difficult to the character damaged.Therefore, when using abrasive substance abrading glass of the present invention etc. to grind the object face, then compare, can grind with the shorter time with using cerium based abrasive material in the past.And, can prevent from more effectively producing damage on the resulting abrasive surface through grinding.As preceding described, in the cerium based abrasive material of the present invention, the weight of Neodymium trioxide accounts for the ratio (Nd of TREO in addition
2O
3/ TREO) scope is 0.001 weight %～5 weight %.Because if less than 0.001 weight %, then easily produce damage, and if surpass 5 weight %, then grinding rate low, also be easy to generate simultaneously and grind damage.This obtains higher performance aspect two and to grind damage at grinding rate, and then the weight of Neodymium trioxide accounts for the ratio (Nd of TREO
2O
3/ TREO) more fortunately below the 2 weight %, better below 0.5 weight %, be preferably in below the 0.1 weight %.
In simple terms, the manufacture method of cerium based abrasive material is: be raw material pulverizing such as the rare earth class carbonate of principal constituent or rare-earth oxide with fluoro-carbon-cerium ore concentrate with the cerium, optionally carry out wet processed such as mineral acid treatment and fluoridation then, then carry out roasting, optionally carry out classification more thereafter and make.The raw material of cerium based abrasive material of the present invention better is rare-earth compounds (for example rare earth class carbonate) or its calcining matter (for example rare-earth oxide) of the low neodymium that obtains by the following method, described method is: to fluoro-carbon-cerium ore concentrate, monazite concentrate, rare earth class concentrate such as China's complicated ore concentrate carry out following a series of processing, be processing and processing such as fractional precipitation processing or substep dissolution process such as vitriolization or alkaline purification, after acquisition has reduced the rare earth class solution of the impurity beyond the rare earth element, utilize solvent extraction and separation to make with extra care this solution, obtain low neodymium rare earth class solution (refined liquid).And then, that is, should hang down neodymium rare earth class solution and precipitant mix such as bicarbonate of ammonia, ammoniacal liquor through following a series of processing, and generate throw out, utilize thereafter to filter to wait this throw out is isolated, finally make the rare-earth compounds of low neodymium.Made with extra care the Nd of the rare earth class solution (refined liquid) that forms by solvent extraction and separation in the past
2O
3/ TREO is usually more than 10 weight %, but as the present invention, by at refining Nd
2O
3/ TREO be the cerium based abrasive material of the value in the specialized range use raw material the time carry out solvent extraction, further reduce the rare earth class of neodymium and the rare earth side heavier than neodymium, obtain low neodymium rare earth class solution (for example, Nd
2O
3The solution of/TREO below 5 weight %) even more ideal.
Cerium based abrasive material of the present invention better is that the gross weight of the rare-earth oxide of cerium, lanthanum, praseodymium and neodymium accounts for the ratio of TREO more than 97 weight %.Because like this, can guarantee high grinding rate more and prevent to produce the effect of damage.If further guarantee to obtain these effects again, better more than 98 weight %, the spy is fortunately more than the 99 weight % for the value of this ratio.
If the more suitable separately containing ratio of each rare-earth oxide among the explanation TREO, then following each rare-earth oxide of explanation: the weight of cerium oxide accounts for the ratio (CeO of TREO
2/ TREO) be preferably 50 weight %～90 weight %.Cerium oxide is the material that has grinding in all rare-earth oxides most, if its part by weight less than lower value, then can not obtain sufficient grinding rate.And if surpass higher limit, then in the feed purification operation, lanthanum must be reduced to enough low etc., the expense that wastes time and energy cost, production rate variance.Based on above-mentioned situation, the ratio that the weight of cerium oxide accounts for TREO is 55 weight %～85 weight %, particularly preferably 60 weight %～80 weight % more preferably.
The weight of lanthanum trioxide accounts for the ratio (La of TREO
2O
3/ TREO) be preferably 2 weight %～45 weight %.Lanthanum trioxide is considered to be in the material that has the fluorine confining force in all rare-earth oxides most, and being present in the cerium is in the rare-earth oxide of principal constituent, and with oxyfluoride (LaOF and CeLa
2O
3F
3) state be present in the cerium based abrasive material.Slowly emit fluoride ion by the fluorine composition of fluorine lanthanum trioxide maintenances such as (LaOF) when grinding, particularly at abrading glass the time, promote chemical action, have the effect that improves grinding rate.But, if the weight of lanthanum trioxide accounts for the ratio of TREO less than above-mentioned lower value, the stable effect of above-mentioned chemical action is weakened, the abrasive surface that grinds gained becomes coarse on the contrary.On the other hand, if surpass higher limit, then can not obtain sufficient grinding rate.In view of the situation, the weight of the lanthanum trioxide ratio more preferably 5 weight %～40 weight %, the particularly preferably 10 weight %～37.5 weight % that account for TREO.In addition, the weight of Praseodymium trioxide accounts for the ratio (Pr of TREO
6O
11/ TREO) be preferably 0.1 weight %～10 weight %, more preferably 1 weight %～8 weight %.
Fluorine containing ratio in the cerium based abrasive material is preferably 0.5 weight %～10 weight %.If less than lower value, then may can not get sufficient grinding rate, and if, then easily produce and grind damage above higher limit.If at grinding rate with grind damage this obtains better effect aspect two, the fluorine containing ratio is 1 weight %～8 weight % more preferably, particularly preferably 2 weight %～7 weight %.
In addition, the contained fluorine (F) and the mol ratio (F/ (La+Pr)) of lanthanum (La) and praseodymium (Pr) are preferably 0.2～3 in the cerium based abrasive material.If less than lower value, then, easily generate oxyhydroxide when particularly grinding in cerium based abrasive material when keeping and when grinding.Generation has the abrasive substance under the state of oxyhydroxide to have the low shortcoming of grinding rate (abrasive power).Also have,, then have the problem that grinding rate will be slack-off in the beginning back short period of time of grinding if in grinding, generate oxyhydroxide easily.And aforementioned molar ratio surpasses the abrasive substance of higher limit, then exists the chemical action of fluorine when grinding strong excessively, the coarse problem of the abrasive surface that obtains after the grinding.
The cerium based abrasive material that meets the following conditions is even more ideal, promptly utilizes and adopts Cu-K alpha-ray or Cu-K α
1When ray was measured the X ray peak intensity as the X-ray diffraction method of x-ray source, the strength ratio (rare earth class oxyfluoride/cerium oxide) that appears at X ray peak intensity the strongest in the X ray peak intensity of X ray peak intensity the strongest in the X ray peak intensity of rare earth class oxyfluoride of 2 θ (diffraction angle)=20 degree (deg)～30 degree (deg) scope and cerium oxide was 0.05～0.6.Here said rare earth class oxyfluoride (LnOF) for example can exemplify fluorine lanthanum trioxide (LaOF) etc.In addition, the X ray peak intensity of said cerium oxide more particularly is meant with the cerium to be cube brilliant rare-earth oxide (Ln of principal constituent here
xO
y) diffraction X ray peak intensity.Ln
xO
yCommon 1.5≤y/x≤2 for example are accredited as CeO
2, Ce
0.5Nd
0.5O
1.75Or Ce
0.75Nd
0.25O
1.875At Nd
2O
3Little but the Ln of/TREO
2O
3In the big abrasive substance of/TREO, Ln
xO
yBe accredited as Ce-Nd-O based compound (Ce
0.5Nd
0.5O
1.75Or Ce
0.75Nd
0.25O
1.875).In this case, can infer the Ln that is accredited as the Ce-Nd-O based compound
xO
yIt is the oxide compound that also contains Ce and Nd rare earth element (La etc.) in addition.
Above-mentioned strength ratio is found to take place easily grinding is caused dysgenic orange peel phenomenon during less than lower value, and is undesirable.And if above higher limit, then grinding rate descends.In view of the situation, aforementioned strength ratio more preferably 0.1～0.5, particularly preferably 0.2～0.4.
Above-mentioned X-ray diffraction is measured, in brief be with above-mentioned characteristic X-ray incident sample (cerium based abrasive material), the edge is the circular scan detector (counter tube or semiconductor detector) at center with the sample, measure the intensity of the X ray of diffraction simultaneously, analyze resulting X-ray diffraction intensity curve, carry out the evaluation of material etc.For example, adopt Cu-K alpha-ray or Cu-K α
1Ray is during as x-ray source, is that the maximum diffraction X ray peak intensities of the rare earth class oxyfluoride in 20 degree～30 degree scopes appear in the scope of 26.5 degree ± 0.5 degree usually in diffraction angle (2 θ), and the cerium oxide (CeO in same scope
2) maximum X ray peak intensity appear at 28.1 the degree ± 1.0 the degree scopes in.
In addition, in the diffraction X ray peak intensity that records by above-mentioned X-ray diffraction assay method, if, the then maximum peak of 2 θ (diffraction angle)=24.2 degree ± 0.5 degree scope, i.e. the X ray peak intensity and the CeO of rare earth class fluorochemical
2The X ray peak intensity in the strength ratio (LnF of the strongest X ray peak intensity
3/ CeO
2) preferably less than 0.04.Because this strength ratio is when this numerical value is above, many easily the generation ground damage.Here said rare earth class fluorochemical (LnF
3) for example can exemplify lanthanum fluoride (LaF
3).Though being the maximum peak of the rare earth class fluorochemical in 20 degree～30 degree scopes, diffraction angle (2 θ) appears at position near the maximum peak of cerium oxide, rather than in the scope of 24.2 degree ± 0.5 degree, but owing to be subjected to the influence of the maximum peak of cerium oxide, be difficult to accurately to judge the intensity etc. of the maximum peak of rare earth class fluorochemical sometimes.Therefore in the present invention, with regard to the rare earth class fluorochemical, use the maximum peak of 24.2 degree ± 0.5 degree scope.
Used target can use the most frequently used copper (Cu), molybdenum (Mo), iron (Fe), cobalt (Co), tungsten (W), silver (Ag) etc. in X-ray diffraction is measured, but will obtain maximum peak intensity, measures more accurately, preferably the copper target.
The pore volume of cerium based abrasive material is preferably 0.002cm
3/ g～0.1cm
3/ g, more preferably 0.005cm
3/ g～0.08cm
3/ g.Because if less than lower value, though damage takes place to grind easily in then grinding rate increase, and if above higher limit, then grinding rate is low excessively, can not obtain sufficient grinding rate.
Just as described above, cerium based abrasive material of the present invention is that grinding rate is higher, and damage produces abrasive substance still less.Therefore,, compare, can grind with the shorter time, and can prevent from more effectively to damage at abrasive surface with using cerium based abrasive material in the past if come abrading glass etc. to grind the object face with it.
Embodiment
Below, the better embodiment of cerium based abrasive material of the present invention is described.
The 1st embodiment
At first, prepared the highly purified cerium oxide (CeO to burn till respectively in 24 hours condition of 850 ℃ of following roastings
2), lanthanum trioxide (La
2O
3), Praseodymium trioxide (Pr
6O
11), Neodymium trioxide (Nd
2O
3), Samarium trioxide (Sm
2O
3).The containing ratio of the impurity beyond each rare-earth oxide middle-weight rare earths type oxide of preparing is less than 0.1%.The purity of any rare-earth oxide (part by weight of the object rare-earth oxide among the TREO) all is more than the 99.99 weight %, in the rare-earth oxide of preparing, the ratio (Nd of the weight of the neodymium in each rare-earth oxide except that Neodymium trioxide in TREO
2O
3/ TREO) less than 0.001%.In addition, the containing ratio of fluorine (F) is less than 0.001 weight %.Prepare to take by weighing in right amount the raw material 10g that these rare-earth oxides mix.So in the present embodiment, for different various cerium based abrasive materials such as the containing ratio of cerium oxide, lanthanum trioxide, Praseodymium trioxide, Neodymium trioxide etc. being carried out the evaluation of nonferromagnetic substance etc., modulated raw material by mixing highly purified rare-earth oxide.Since can think each rare-earth oxide in the raw material containing ratio with make after the TREO of abrasive substance in the part by weight of each rare-earth oxide be identical, so do not illustrate these containing ratios numerical value (reference table 1).This external comparative example 1 does not have the mixed oxidization neodymium in the raw material.Also have, in the embodiment of table 1 6～embodiment 8, (CeO
2+ La
2O
3+ Pr
6O
11+ Nd
2O
3)/TREO (4 kinds of totals) does not reach 100%, is mixed with Samarium trioxide in this expression raw material.
The raw material (mixture of rare-earth oxide) that makes is mixed with the pure water of 2 times of weight of this raw material weight, carry out wet pulverization with attritor (attritor) and obtained slurry.The stainless steel abrading-ball that has used diameter 5mm in attritor is as crushing medium.In addition, the pulverizing time is 8 hours.
Then, in the slurry that obtains, add 10% hydrofluoric acid, adjust the weight ratio (F/ (TREO+F)) of the fluorine composition in the slurry, this slurry is carried out 30 minutes stirring (fluoridation).In each embodiment and each comparative example, the weight ratio (F/ (TREO+F)) of fluorine composition has been modulated to 6% except comparative example 5,6 except embodiment 12,13.And in embodiment 12, embodiment 13, comparative example 6, then adjusted the weight ratio of fluorine composition respectively according to 1.5%, 10%, 15% ratio.In addition, in comparative example 5, do not carry out this fluoridation.
, make solid formation divide sedimentation, extract supernatant liquor, add the so-called repulp washing of pure water, then adopt filter press technique to filter the slurry after cleaning thereafter.Then, under 140 ℃ with the filtration cakes torrefaction that obtains 48 hours.Decompose the dry cake obtain with roller crusher more thereafter, with the broken thing that obtains 950 ℃ of roastings 18 hours.This calcining matter is pulverized with experiment pulverizer (sample mill), and then utilized turbine classifier that the crushed material that obtains is carried out classification (the classification point is set at 3 μ m), just made cerium based abrasive material.The part by weight of each rare-earth oxide of prepared cerium based abrasive material in TREO is shown in table 1.
The mensuration of fluorine concentration
To prepared cerium based abrasive material in each embodiment and the comparative example, measure its fluorine containing ratio.In the mensuration of fluorine concentration, except the abrasive substance that comparative example 5 makes, alkali fusion warm water extraction fluoride ion electrode method has been adopted in the fluorine analysis.The mensuration of the fluorine concentration of the abrasive substance that is made by comparative example 5 has adopted thermal hydrolysis lanthanum alizarin (alizarin) complexon (trade(brand)name of complexon ammonia carboxylic coordination agent) absorption photometry in addition.Measurement result is shown in each table.
Grinding test
The cerium based abrasive material that uses each embodiment and comparative example to make carries out grinding test, the damage evaluation of the abrasive surface that carried out grinding rate, is obtained and detergency evaluation.Evaluation result is shown in each table.
At first, pulverous cerium based abrasive material powder and pure water are mixed the abrasive substance slurry that to have modulated solid formation branch concentration be 15 weight %.Use this abrasive substance slurry, utilize rub tester (HSP-2I type, Tai East Jing Machine (Co., Ltd.) system), the flat panel of 65mm φ is ground with the surface of glass.After grinding end, clean flat panel glass, under dustless state, make its drying then with pure water.This rub tester is that with the instrument of grinding pad grinding object face, grinding pad has used the grinding pad of urethane system when grinding object face supply abrasive substance slurry.Grinding pad is set at 5.9kPa (60g/cm to the pressure of abrasive surface
2).The speed of rotation of rub tester is set at 100rpm.The feed rate of abrasive substance slurry is 5 liters/minute.
The evaluation of grinding rate
Measure the glass weight before and after grinding, obtain the reduction of grinding the back glass weight, tried to achieve the grinding value according to this value.In this grinding test, utilize this grinding value that grinding rate is estimated.Grinding value when grinding with the abrasive substance that adopts comparative example 3 to make here in addition, is benchmark (100).
Grind the evaluation of damage
After grinding end, clean abrasive surface, make its drying under the dustless state, this abrasive surface is damaged evaluation with pure water.Damage evaluation is carried out in the following manner, promptly adopts the reflection method that the halogen lamp of 300,000 Luxs is used as light source, and the sight glass surface with the quantity fractionation of big damage and microlesion, is divided into full marks, the evaluation of deducting points with 100.During this damage is estimated, with hard disk with or the finishing polish of the glass substrate used of LCD grind desired grinding precision as judgment standard.Specifically, in table 1～table 4, " ◎ " expression (was highly suitable for HD uses glass substrate with LCD finishing polish) more than 98 minutes, " zero " expression less than 98 minutes, more than or equal to 95 minutes (be applicable to HD with LCD with the finishing polish of glass substrate), " △ " expression less than 95 minutes, more than or equal to 90 minutes (can be used for HD with LCD with the finishing polish of glass substrate), " * " expression was less than 90 minutes (be not useable for HD with the finishing polish of LCD with glass substrate).
The evaluation of detergency
Detergency with regard to abrasive substance is tested.In detergency is estimated, at first, to be immersed in the abrasive substance slurry with slide glass through cleaning, exsiccant observation by light microscope, after the taking-up, make its complete drying, it is immersed in the container that pure water is housed thereafter at 50 ℃, carry out 5 minutes ultrasonic cleaning, after the ultrasonic cleaning, the slide glass pure water rinsing with taking out has from container obtained object of observation slide glass.Then, the remaining quantity of the abrasive substance particle by remaining in slide surface with observation by light microscope has been estimated detergency.Specifically, in table 1～table 4, it is remaining that the abrasive substance particle has not been observed in " zero " expression, be suitable for use in very much finishing polish, " △ " is though that the abrasive substance particle has been observed in expression is remaining but few, be suitable for use in finishing polish, remaining very many abrasive substance particles that has are observed in " * " expression, are not suitable for being used in finishing polish.
Table 1
| Cerium based abrasive material | Nonferromagnetic substance | |||||||||
| ※ 1) fluorine containing ratio (wt%) | ※ 2) TREO converted weight (wt%) | Grinding rate | Damage is estimated | Detergency | ||||||
| The ratio of the weight of each rare-earth oxide in the TREO converted weight (wt%) | ||||||||||
| ??CeO 2 | ??La 2O 3 | ??Pr 6O 11 | ??Nd 2O 3 | 4 kinds of totals | ||||||
| Comparative example 1 | ??5.3 | ??94.5 | ??65.0 | ??31.0 | ??4.0 | ??＜0.001 | ??100 | ??128 | ??△ | ??△ |
| Embodiment 1 | ??5.2 | ??94.5 | ??65.0 | ??30.99 | ??4.0 | ??0.01 | ??100 | ??152 | ??◎ | ??○ |
| Embodiment 2 | ??5.2 | ??94.7 | ??65.0 | ??30.9 | ??4.0 | ??0.1 | ??100 | ??145 | ??◎ | ??○ |
| Embodiment 3 | ??5.2 | ??94.5 | ??65.0 | ??30.5 | ??4.0 | ??0.5 | ??100 | ??138 | ??◎ | ??○ |
| Embodiment 4 | ??5.2 | ??94.5 | ??65.0 | ??30.0 | ??4.0 | ??1.0 | ??100 | ??132 | ??◎ | ??○ |
| Embodiment 5 | ??5.2 | ??94.3 | ??65.0 | ??28.0 | ??4.0 | ??3.0 | ??100 | ??121 | ??○ | ??○ |
| Comparative example 2 | ??5.1 | ??94.4 | ??65.0 | ??25.0 | ??4.0 | ??6.0 | ??100 | ??103 | ??△ | ??△ |
| Comparative example 3 | ??4.9 | ??94.1 | ??65.0 | ??21.0 | ??4.0 | ??10.0 | ??100 | ??100 | ??△ | ??△ |
| Embodiment 3 | ??5.2 | ??94.5 | ??65.0 | ??30.5 | ??4.0 | ??0.5 | ??100 | ??138 | ??◎ | ??○ |
| Embodiment 6 | ??5.2 | ??94.4 | ??65.0 | ??29.5 | ??4.0 | ??0.5 | ??99.0 | ??134 | ??◎ | ??○ |
| Embodiment 7 | ??5.2 | ??94.5 | ??65.0 | ??28.5 | ??4.0 | ??0.5 | ??98.0 | ??129 | ??◎ | ??○ |
| Embodiment 8 | ??5.2 | ??94.3 | ??65.0 | ??26.5 | ??4.0 | ??0.5 | ??96.0 | ??118 | ??○ | ??○ |
| Embodiment 9 | ??5.8 | ??93.9 | ??40.0 | ??47.0 | ??12.0 | ??1.0 | ??100 | ??120 | ??○ | ??○ |
| Embodiment 4 | ??5.2 | ??94.5 | ??65.0 | ??30.0 | ??4.0 | ??1.0 | ??100 | ??132 | ??◎ | ??○ |
| Embodiment 10 | ??4.3 | ??95.1 | ??80.0 | ??15.0 | ??4.0 | ??1.0 | ??100 | ??147 | ??◎ | ??○ |
| Embodiment 11 | ??2.5 | ??97.0 | ??95.0 | ??3.0 | ??1.0 | ??1.0 | ??100 | ??135 | ??○ | ??△ |
| Embodiment 5 | ??5.2 | ??94.3 | ??65.0 | ??28.0 | ??4.0 | ??3.0 | ??100 | ??121 | ??○ | ??○ |
| Comparative example 4 | ??5.2 | ??94.0 | ??65.0 | ??32.0 | ??0 | ??3.0 | ??100 | ??104 | ??△ | ??△ |
※ 1) fluorine element weight accounts for the ratio of abrasive substance weight
※ 2) the TREO converted weight is to the ratio of abrasive substance weight
As shown in table 1, the abrasive substance of embodiment 1～5 and comparative example 1～3, the Neodymium trioxide (Nd among its TREO
2O
3) part by weight have nothing in common with each other.Wherein, the abrasive substance grinding rate height of embodiment 1～5, grinding damage are difficult to take place.Relative therewith, the abrasive substance of the comparative example 1 of unmixed Neodymium trioxide is though the grinding rate height easily produces and grinds damage.In addition, the part by weight of the Neodymium trioxide among the TREO surpasses low, the also easily generation grinding damage simultaneously of abrasive substance grinding rate of comparative example 2 and the comparative example 3 of 5 weight %.These results show that the weight of the Neodymium trioxide in the cerium based abrasive material accounts for the ratio (Nd of TREO
2O
3/ TREO) be preferably 0.001 weight %～5 weight %.With regard to grinding rate, each embodiment is compared as can be known, below the 2 weight %, better below 0.5 weight %, the spy is fortunately below the 0.1 weight % more fortunately for the part by weight of the neodymium among the TREO.
In the abrasive substance of embodiment 6～8,4 oxide compounds [cerium oxide (CeO
2), lanthanum trioxide (La
2O
3), Praseodymium trioxide (Pr
6O
11), Neodymium trioxide (Nd
2O
3)] gross weight account for the ratio of TREO all below 100 weight %, the value of this ratio of each embodiment is that containing ratio has nothing in common with each other, from the embodiment 1～8 that contains these embodiment as can be known, if the ratio of gross weight is 96 weight %, the grinding rate that abrasive substance is required can be guaranteed, and the grinding damage can be prevented to produce.If total containing ratio then can be guaranteed higher grinding rate more than 97 weight %, and can prevent to produce damage more effectively.
Embodiment 4 and embodiment 10, not only Neodymium trioxide accounts for the ratio (Nd of TREO
2O
3/ TREO) be the ideal value, and CeO
2/ TREO, La
2O
3/ TREO, Pr
6O
11/ TREO also is the ideal value, and the grinding rate height can not take place to grind damage substantially, and it is remaining not observed abrasive substance.In contrast, though embodiment 9 and embodiment 11 are Nd
2O
3/ TREO is the ideal value, but CeO
2/ TREO, La
2O
3/ TREO, Pr
6O
11Have at least 1 value undesirable among the/TREO, so have at least one to be inferior to embodiment 4 and embodiment 10 in the grinding rate, grinding damage, detergency.But, with Nd
2O
3It is still good that/TREO is that the comparative example 1～comparative example 3 of unfavorable value is compared.The abrasive substance of comparative example 4 does not contain praseodymium fully, therefore because Pr
6O
11The value of/TREO is undesirable, and nonferromagnetic substance is inferior to embodiment 5.
According to the fluorine in the cerium based abrasive material and each rare earth class molar weight (mol/L), calculated the mol ratio (F/ (La+Pr)) of total containing ratio of fluorine containing ratio in the cerium based abrasive material and lanthanum and praseodymium at every 1kg abrasive substance.The value of calculating is shown in table 2.The CeO of the cerium based abrasive material of embodiment shown in the table 2 and comparative example
2/ TREO is 65.0 weight %, La
2O
3/ TREO is 30.9 weight %, Pr
6O
11/ TREO is 4.0 weight %, Nd
2O
3/ TREO is 0.1 weight %.
Table 2
| Abrasive substance | The molar weight of every 1kg abrasive substance (mol/kg) | Mol ratio | Nonferromagnetic substance | |||||||||
| ※ 1) fluorine containing ratio (wt%) | ※ 2) TREO converted weight (wt%) | ??F | ??La | ??Pr | ??Nd | ??La/ ??Pr | ??Nd/ ??Pr | ??F/ ??La+Pr | Grinding rate | Damage is estimated | Detergency | |
| Comparative example 5 | ??＜0.001 | ??99.8 | ??＜0.005 | ??1.89 | ??0.234 | ??0.006 | ??8.09 | ??0.03 | ??＜0.001 | ??35 | ??○ | ??× |
| Embodiment 12 | ??1.2 | ??98.4 | ??0.63 | ??1.87 | ??0.231 | ??0.006 | ??8.08 | ??0.03 | ??0.30 | ??123 | ??◎ | ??○ |
| Embodiment 2 | ??5.1 | ??94.7 | ??2.68 | ??1.80 | ??0.223 | ??0.006 | ??8.05 | ??0.03 | ??1.33 | ??145 | ??◎ | ??○ |
| Embodiment 13 | ??8.4 | ??91.0 | ??4.42 | ??1.73 | ??0.214 | ??0.005 | ??8.07 | ??0.03 | ??2.28 | ??163 | ??○ | ??○ |
| Comparative example 6 | ??12.5 | ??87.9 | ??6.58 | ??1.67 | ??0.207 | ??0.005 | ??8.05 | ??0.03 | ??3.51 | ??166 | ??× | ??△ |
※ 1) fluorine element weight accounts for the ratio of abrasive substance weight
※ 2) the TREO converted weight is to the ratio of abrasive substance weight
As shown in table 2, the abrasive substance of embodiment 2,12,13 and comparative example 5,6, the containing ratio of the fluorine in the abrasive substance (F) has nothing in common with each other.Wherein, the abrasive substance grinding rate height of embodiment 2,12,13, and be difficult for taking place to grind damage, be good abrasive substance.And in contrast, the grinding rate of abrasive substance of comparative example 5 that contains fluorine hardly is obviously on the low side.In addition, the abrasive substance grinding rate height of the comparative example 6 that the fluorine containing ratio is high, but damage takes place to grind easily.This result shows that the fluorine containing ratio in the cerium based abrasive material is preferably 0.5 weight %～10 weight %.Will and grind at grinding rate and obtain better effect in the damage, the fluorine containing ratio is 2 weight %～7 weight % more preferably.Also have, the mol ratio of total containing ratio of fluorine containing ratio and lanthanum and praseodymium (F/ (La+Pr)) is preferably 0.2～3.
The 2nd embodiment
Describe using with better embodiment at the cerium based abrasive material of the present invention of the different raw material manufacturing of the used raw material of embodiment 1.
At first, having prepared is the rare earth class carbonate (in homemade) of principal constituent with the cerium.In this rare earth class carbonate, TREO is 52.3 weight %, CeO
2/ TREO is 52.1%, La
2O
3/ TREO is 26.7%, Pr
6O
11/ TREO is 7.2%, Nd
2O
3/ TREO is 13.0%.In the embodiment 14～17 of present embodiment and the comparative example 7～10 (with reference to aftermentioned table 3 and table 4), comparative example 7 directly uses this rare earth class carbonate as raw material.In embodiment 14～17 and the comparative example 8～10, made the rare earth class carbonate (Nd that is used as raw material through following processing
2O
3/ TREO is 0.1 weight %～6.3 weight %): with this rare earth class carbonate of dissolving with hydrochloric acid, adopt the refining resulting carbonate solution of Solvent Extraction Separation, obtained reducing the rare earth class solution (refined liquid) of neodymium and lanthanum, the rare earth class solution and the ammonium bicarbonate aqueous solution (precipitation agent) of gained are mixed, generate the post precipitation of rare earth class carbonate, filter, wash and make with separating centrifuge.
Here, brief description is carried out in the solvent extraction of present embodiment.In this solvent extraction, organic solvent adopts by extraction agent (PC-88A: big eight chemical industry are made) and thinner (イ プ ゾ-Le: be the organic solvent that 1/2 mixed forms according to liquid measure than (extraction agent/thinner) bright dipping petroleum chemistry system).Be under 8/1 the state, to make this organic solvent and carbonate solution (TREO240g/L) convection current MULTI CONTACT (30 grades) in throughput ratio (organic solvent/carbonate solution), rare earth element is extracted in the organic solvent.At this moment, a part of lanthanum is remained in the aqueous solution.Embodiment in addition and comparative example are that the rare earth element that will almost all measure all is extracted in the organic solvent.The adjustment of extraction can be undertaken by the interpolation flow that changes the aqueous sodium hydroxide solution that is added in the process of convection current multi-stage solvent extraction.After this, make the organic solvent and the 3mol/L aqueous hydrochloric acid convection current MULTI CONTACT (30 grades) of rear earth containing element, stay the organic solvent with neodymium with than the easier major part of neodymium by the rare earth element of organic solvent extraction (heavy rare earths and the yttrium (Y) that begin from samarium), the neodymium of most lanthanum, cerium, praseodymium and a part is extracted in the aqueous hydrochloric acid, has made refined liquid.The adjustment of extraction quantity can be carried out (flow of organic solvent is fixed) by the flow that changes aqueous hydrochloric acid.
Adopt and the raw material (rare earth class carbonate) of gained has been made cerium based abrasive material with embodiment 1 identical operation.From the above as can be known, the words that the raw material of the 2nd embodiment is compared with the raw material of the 1st embodiment, the ratio of TREO in the raw material and raw material gross weight is low, also the same in embodiment 2 with embodiment 1, to carrying out case of wet attrition, obtained slurry with attritor by the pure water of 2 times of weight of raw material weight and the mixture that raw material mixes.The time of adopting attritor to carry out case of wet attrition is 10 hours.In by the slurry of case of wet attrition gained, add in the fluoridation of 10% hydrofluoric acid, reach 7% according to the weight ratio that makes the fluorine composition in the slurry (F/ (TREO+F)) and modulate.Maturing temperature in the calcining process except embodiment 17,18 and comparative example 9,10, is all 950 ℃ mutually with embodiment 1.In addition, maturing temperature is: comparative example 9 is that 650 ℃, embodiment 17 are that 750 ℃, embodiment 18 are that 1100 ℃, comparative example 10 are 1200 ℃.It is identical with embodiment 1 that abrasive substance is in addition created conditions.Therefore omit the explanation of abrasive substance manufacturing process here.
Table 3
| Cerium based abrasive material | Nonferromagnetic substance | |||||||||
| ※ 1) fluorine containing ratio (wt%) | ※ 2) TREO converted weight (wt%) | Grinding rate | Damage is estimated | Detergency | ||||||
| The ratio of the weight of each rare-earth oxide in the TREO converted weight (wt%) | ||||||||||
| ??CeO 2 | ??La 2O 3 | ??Pr 6O 11 | ??Nd 2O 3 | 4 kinds of totals | ||||||
| Comparative example 7 | ??6.5 | ??92.0 | ??52.1 | ??26.7 | ??7.2 | ??13.0 | ??99.0 | ??95 | ??△ | ??△ |
| Comparative example 8 | ??6.3 | ??92.5 | ??58.5 | ??30.2 | ??4.5 | ??6.3 | ??99.5 | ??102 | ??△ | ??△ |
| Embodiment 14 | ??6.4 | ??92.6 | ??60.4 | ??31.5 | ??3.6 | ??4.2 | ??99.7 | ??120 | ??○ | ??○ |
| Embodiment 15 | ??6.1 | ??93.0 | ??63.7 | ??33.6 | ??2.3 | ??0.2 | ??99.8 | ??131 | ??◎ | ??○ |
| Embodiment 16 | ??5.7 | ??93.3 | ??79.5 | ??19.6 | ??0.7 | ??0.1 | ??99.9 | ??142 | ??◎ | ??○ |
※ 1) fluorine element weight accounts for the ratio of abrasive substance weight
※ 2) the TREO converted weight is to the ratio of abrasive substance weight
Though the Nd of the rare earth class carbonate of the initial feed of the 2nd embodiment (in homemade)
2O
3/ TREO surpasses 5%, but has reduced the abrasive substance (Nd of the embodiment 14～16 of neodymium through solvent extraction
2O
3/ TREO is below 5%) obtained the high abrasive energy.Relative therewith, Nd
2O
3/ TREO surpasses the abrasive substance of 5% comparative example 7,8 and compares with the abrasive substance of embodiment, grinding rate, damage estimate and detergency poor.
To the cerium based abrasive material that makes, diffraction X ray intensity (Intensity), median size (D have been carried out
50), the mensuration of pore volume.
X-ray diffraction is measured
Use X-ray diffraction device (マ Star Network サ イ エ Application ス (Co., Ltd.) system, MXP18), cerium based abrasive material is carried out X-ray diffraction analysis, measured diffraction X ray intensity.In this is measured, to using copper (Cu) target, the Cu-K α of irradiation Cu-K alpha-ray gained
1Resolve at the peak that appears at diffraction angle (2 θ)=20 degree～30 degree in the diffraction X-ray pattern of ray.Other condition determination is, tube voltage 40kV, tube current 150mA, measurement range 2 θ=5～80 degree, sampling width 0.02 degree, sweep velocity 4 degree/minute.The X ray peak intensity and the lanthanum fluoride (LaF of the fluorine lanthanum trioxide (LaOF) that reads from the X-ray diffraction measurement result of the cerium based abrasive material of each embodiment and comparative example
3) the X ray peak intensity to cerium oxide (CeO
2) the data of ratio of X ray peak intensity be shown in table 4.
Median size (D
50) mensuration
Use laser diffraction and scattering method particle size distribution device ((Co., Ltd.) Shimadzu Seisakusho Ltd. system: SALD-2000A), measure the size-grade distribution of cerium based abrasive material, obtained median size (D
50: the particle diameter when the small particle size side begins to be accumulated to volume 50%).
The mensuration of pore volume
Use pore volume determinator (COULTER SA3100), measured the pore volume of cerium based abrasive material.
Table 4
| Cerium based abrasive material | X ray peak intensity ratio | The abrasive substance rerum natura | Nonferromagnetic substance | ||||||||||
| ※ 1) fluorine containing ratio (wt%) | ※ 2) TREO converted weight (wt%) | ??LaOF ??/ ??CeO 2 | ??LaF 3??/ ??CeO 2 | Median size (D 50) ??(μm) | Pore volume (m3/g) | Grinding rate | Damage is estimated | Detergency | |||||
| The ratio of the weight of each rare-earth oxide in the TREO converted weight (wt%) | |||||||||||||
| ??CeO 2 | ??La 2O 3 | ??Pr 6O 11 | ??Nd 2O 3 | ||||||||||
| Comparative example 9 | ??6.7 | ??93.0 | ??63.7 | ??33.6 | ??2.3 | ??0.2 | ??0.02 | ??0.05 | ??0.47 | ??0.132 | ??25 | ??△ | ??× |
| Embodiment 17 | ??6.4 | ??93.0 | ??63.7 | ??33.6 | ??2.3 | ??0.2 | ??0.15 | ??＜0.01 | ??0.69 | ??0.092 | ??115 | ??◎ | ??○ |
| Embodiment 15 | ??6.1 | ??93.0 | ??63.7 | ??33.6 | ??2.3 | ??0.2 | ??0.27 | ??＜0.01 | ??0.97 | ??0.047 | ??131 | ??◎ | ??○ |
| Embodiment 18 | ??5.7 | ??93.0 | ??63.7 | ??33.6 | ??2.3 | ??0.2 | ??0.43 | ??＜0.01 | ??1.27 | ??0.0055 | ??155 | ??○ | ??○ |
| Comparative example 10 | ??5.2 | ??93.0 | ??63.7 | ??33.6 | ??2.3 | ??0.2 | ??0.72 | ??＜0.01 | ??2.05 | ??0.0009 | ??163 | ??× | ??○ |
※ 1) fluorine element weight accounts for the ratio of abrasive substance weight
※ 2) the TREO converted weight is to the ratio of abrasive substance weight
In the abrasive substance of embodiment shown in the table 4 and comparative example, the strength ratio (LaOF/CeO of X ray peak intensity
2) be the abrasive substance grinding rate height of 0.05～0.6 embodiment and be difficult to take place to grind damage, be good abrasive substance.In contrast, strength ratio (LaOF/CeO
2) the abrasive substance grinding rate of little comparative example 9 is obviously on the low side, and damage has taken place.In addition, though the abrasive substance grinding rate height of the big comparative example 10 of strength ratio has produced than obvious impairment.This result shows, the strength ratio (LaOF/CeO of X ray peak intensity
2) be that 0.05～0.6 abrasive substance is an ideal.
Pore volume is 0.002cm
3/ g～0.1cm
3The abrasive substance grinding rate height of the embodiment of/g and be difficult to take place to grind damage is good abrasive substance.The grinding rate of the abrasive substance of the comparative example 9 that in contrast, pore volume is big is obviously on the low side.Also have, damage has taken place in the abrasive substance of the comparative example 10 that pore volume is little.This result shows that pore volume is 0.002cm
3/ g～0.1cm
3The abrasive substance of/g is an ideal.
The possibility of industrial utilization
Cerium based abrasive material of the present invention is that grinding rate is higher, and grinding-material still less occurs in damage. Come the grinding object faces such as abrading glass with this cerium based abrasive material, compare with using cerium based abrasive material in the past, can grind the enough shorter time, and can prevent from more effectively producing damage at abradant surface. Therefore, be suitable for very much the surface grinding of precision instrument, electronic equipment or their parts etc.
Claims (7)
1, cerium based abrasive material, it is to be the cerium based abrasive material of principal constituent with fluorine (F) and rare-earth oxide, contained rare earth element has cerium (Ce), lanthanum (La), praseodymium (Pr) and neodymium (Nd) at least in the described rare-earth oxide, it is characterized in that the weight of Neodymium trioxide accounts for the ratio (Nd of total rare earth (TRE) type oxide converted weight (TREO)
2O
3/ TREO) be 0.001 weight %～5 weight %.
2, cerium based abrasive material according to claim 1 is characterized in that, the gross weight of the rare-earth oxide of cerium, lanthanum, praseodymium and neodymium accounts for the ratio of total rare earth (TRE) type oxide converted weight more than 97 weight %.
3, cerium based abrasive material according to claim 1 and 2 is characterized in that, the weight of cerium oxide accounts for the ratio (CeO of total rare earth (TRE) type oxide converted weight
2/ TREO) be 50 weight %～90 weight %; The weight of lanthanum trioxide accounts for the ratio (La of total rare earth (TRE) type oxide converted weight
2O
3/ TREO) be 2 weight %～45 weight %; The weight of Praseodymium trioxide accounts for the ratio (Pr of total rare earth (TRE) type oxide converted weight
6O
11/ TREO) be 0.1 weight %～10 weight %.
According to each described cerium based abrasive material in the claim 1～3, it is characterized in that 4, the containing ratio of fluorine is 0.5 weight %～10 weight %.
According to each described cerium based abrasive material in the claim 1～4, it is characterized in that 5, contained fluorine (F) and contained lanthanum (La) and the mol ratio (F/ (La+Pr)) of praseodymium (Pr) are 0.2～3.
6, according to each described cerium based abrasive material in the claim 1～5, it is characterized in that, utilize and adopt Cu-K alpha-ray or Cu-K α
1When ray was measured the X ray peak intensity as the X-ray diffraction method of x-ray source, the strength ratio (rare earth class oxyfluoride/cerium oxide) that appears at X ray peak intensity the strongest in the X ray peak intensity of X ray peak intensity the strongest in the X ray peak intensity of rare earth class oxyfluoride of 2 θ (diffraction angle)=20 degree～30 degree scopes and cerium oxide was 0.05～0.6.
According to each described cerium based abrasive material in the claim 1～6, it is characterized in that 7, pore volume is 0.002cm
3/ g～0.1cm
3/ g.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP112763/2003 | 2003-04-17 | ||
| JP2003112763 | 2003-04-17 | ||
| PCT/JP2004/003276 WO2004092297A1 (en) | 2003-04-17 | 2004-03-12 | Cerium-based polishing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1701108A true CN1701108A (en) | 2005-11-23 |
| CN100447218C CN100447218C (en) | 2008-12-31 |
Family
ID=33296066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800007749A Expired - Lifetime CN100447218C (en) | 2003-04-17 | 2004-03-12 | Cerium-based polishing material |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4401353B2 (en) |
| KR (1) | KR100697682B1 (en) |
| CN (1) | CN100447218C (en) |
| TW (1) | TWI313707B (en) |
| WO (1) | WO2004092297A1 (en) |
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| CN101899281A (en) * | 2009-05-25 | 2010-12-01 | 甘肃稀土新材料股份有限公司 | Rare earth polishing powder and production method thereof |
| CN101899264A (en) * | 2009-05-25 | 2010-12-01 | 甘肃稀土新材料股份有限公司 | Rare earth polishing powder and preparation method thereof |
| CN103361030A (en) * | 2013-07-23 | 2013-10-23 | 内蒙古科技大学 | Praseodymium-containing ultrafine high-precision rare earth polishing powder and its preparation method |
| CN103509472A (en) * | 2013-10-25 | 2014-01-15 | 上海华明高纳稀土新材料有限公司 | Cerium-based mixed rare earth polishing powder and preparation method thereof |
| CN103923604A (en) * | 2013-01-15 | 2014-07-16 | 安阳市岷山有色金属有限责任公司 | Cerium based abrasive material |
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| CN107603491A (en) * | 2017-10-16 | 2018-01-19 | 淄博包钢灵芝稀土高科技股份有限公司 | Polishing powder from rare earth and preparation method thereof |
| CN108026433A (en) * | 2015-09-25 | 2018-05-11 | 昭和电工株式会社 | Cerium based abrasive material and its manufacture method |
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| TWI338036B (en) * | 2005-04-04 | 2011-03-01 | Showa Denko Kk | Cerium-based oxide abrasive, and producing method and use thereof |
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| JP4273475B2 (en) * | 1999-09-21 | 2009-06-03 | 株式会社フジミインコーポレーテッド | Polishing composition |
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-
2004
- 2004-02-24 TW TW093104559A patent/TWI313707B/en not_active IP Right Cessation
- 2004-03-12 CN CNB2004800007749A patent/CN100447218C/en not_active Expired - Lifetime
- 2004-03-12 JP JP2005505341A patent/JP4401353B2/en not_active Expired - Lifetime
- 2004-03-12 WO PCT/JP2004/003276 patent/WO2004092297A1/en active Application Filing
- 2004-03-12 KR KR1020047019949A patent/KR100697682B1/en active IP Right Grant
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| CN101899281A (en) * | 2009-05-25 | 2010-12-01 | 甘肃稀土新材料股份有限公司 | Rare earth polishing powder and production method thereof |
| CN101899264A (en) * | 2009-05-25 | 2010-12-01 | 甘肃稀土新材料股份有限公司 | Rare earth polishing powder and preparation method thereof |
| CN103923604A (en) * | 2013-01-15 | 2014-07-16 | 安阳市岷山有色金属有限责任公司 | Cerium based abrasive material |
| CN103361030A (en) * | 2013-07-23 | 2013-10-23 | 内蒙古科技大学 | Praseodymium-containing ultrafine high-precision rare earth polishing powder and its preparation method |
| CN103509472A (en) * | 2013-10-25 | 2014-01-15 | 上海华明高纳稀土新材料有限公司 | Cerium-based mixed rare earth polishing powder and preparation method thereof |
| CN108026433A (en) * | 2015-09-25 | 2018-05-11 | 昭和电工株式会社 | Cerium based abrasive material and its manufacture method |
| CN108026433B (en) * | 2015-09-25 | 2021-02-26 | 昭和电工株式会社 | Cerium-based abrasive and method for producing the same |
| CN107556922A (en) * | 2017-09-27 | 2018-01-09 | 甘肃稀土新材料股份有限公司 | A kind of polishing powder from rare earth containing samarium and its preparation technology |
| CN107556922B (en) * | 2017-09-27 | 2020-05-19 | 甘肃稀土新材料股份有限公司 | Samarium-containing rare earth polishing powder and preparation process thereof |
| CN107603491A (en) * | 2017-10-16 | 2018-01-19 | 淄博包钢灵芝稀土高科技股份有限公司 | Polishing powder from rare earth and preparation method thereof |
| CN107603491B (en) * | 2017-10-16 | 2019-08-30 | 淄博包钢灵芝稀土高科技股份有限公司 | Polishing powder from rare earth and preparation method thereof |
| CN110256970A (en) * | 2019-07-06 | 2019-09-20 | 深圳市瑞来稀土材料有限公司 | A kind of polishing powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI313707B (en) | 2009-08-21 |
| TW200426206A (en) | 2004-12-01 |
| KR100697682B1 (en) | 2007-03-20 |
| JPWO2004092297A1 (en) | 2006-07-06 |
| JP4401353B2 (en) | 2010-01-20 |
| CN100447218C (en) | 2008-12-31 |
| KR20050019733A (en) | 2005-03-03 |
| WO2004092297A1 (en) | 2004-10-28 |
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