Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/45—Anti-settling agents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/02—Compounds of alkaline earth metals or magnesium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/02—Compounds of alkaline earth metals or magnesium
  • C09C1/021—Calcium carbonates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/02—Compounds of alkaline earth metals or magnesium
  • C09C1/028—Compounds containing only magnesium as metal
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/40—Compounds of aluminium
  • C09C1/42—Clays
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/63—Inorganic compounds
  • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
• • 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
  • C01P2006/12—Surface area
• • 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
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/36—Coatings with pigments
  • D21H19/38—Coatings with pigments characterised by the pigments

Definitions

• the present invention relates to a process for manufacturing high solids suspensions of mineral materials, the high solids aqueous suspension of mineral materials obtained by this process, as well as the use of such suspensions.
• Such well-known mineral materials comprise for example natural calcium carbonate, synthetic calcium carbonate, and miscellaneous analogous fillers containing calcium carbonates such as dolomite or mixed carbonate based fillers; various matter such as talc or analogues; mica, clay, titanium dioxide, etc.
• the mineral material in the form of high solids suspensions, i.e. containing only little water, which, however, generally is only possible by adding a high amount of dispersing agents or grinding aids.
• dispersing agents water soluble polymers based on partially or totally neutralised polyacrylic acids or their derivatives (EP 0 046 573, EP 0 100 947, EP 0 100 948, EP 0 129 329, EP 0 261 039, EP 0 516 656, EP 0 542 643, EP 0 542 644, EP 0 717 051) to provide aqueous mineral suspensions that meet the desired refinement and low viscosity criteria.
• These dispersing agents have to be used in a high quantity, which is not only not desirable from the economical view, but also disadvantageous with respect to the capability of the final product of developing scattering visible light as required by the end user in paper application.
• WO 02/49766, EP 0 850 685, WO 2008/010055, WO 2007/072168 disclose processes for manufacturing aqueous suspensions of refined mineral material, with a dry matter concentration that can be high, while having a low BrookfieldTM viscosity that remains stable over time.
• EP 0 614 948 describes a process for grinding mineral material at a high solids content clearly indicating that this process is only suitable for suspension having an initial solids content of not more than 70 wt%.
• This object is achieved by a process for manufacturing high solids aqueous suspensions of mineral material(s) comprising the steps of: a) providing at least one mineral material,
• step c) grinding the mineral material of the resulting aqueous suspension of step b), d) concentrating the aqueous suspension of ground mineral material of step c) by flash cooling.
• Mineral materials suitable for the use in the process according to the present invention are preferably selected from the group comprising natural calcium carbonate (GCC) such as marble, chalk, limestone; precipitated calcium carbonate (PCC) such as aragonitic PCC, vateritic PCC and/or calcitic PCC, especially prismatic, rhombohedral or scalenohedral PCC; surface modified calcium carbonate; dolomite; talc; bentonite; clay; magnesite; satin white; sepiolite, huntite, diatomite; silicates; and mixtures thereof.
• GCC natural calcium carbonate
• PCC precipitated calcium carbonate
• aragonitic PCC such as aragonitic PCC, vateritic PCC and/or calcitic PCC, especially prismatic, rhombohedral or scalenohedral PCC
• surface modified calcium carbonate dolomite; talc; bentonite; clay; magnesite; satin white;
• from 40 to 85 wt%, preferably from 45 to 80 wt%, more preferably from 50 to 75 wt%, most preferably from 60 to 70 wt%, e.g. 65 wt% of the at least one mineral material particles provided in step a) have an equivalent spherical diameter of ⁇ 10 pm, measured by means of a Sedigraph 5100 device from the company Micromeritics, USA, in an aqueous solution of 0.1 wt-% Na 4 P 2 0 7 , wherein the samples were dispersed using a high-speed stirrer and ultrasound.
• an aqueous suspension is prepared from the mineral material provided in step a).
• This aqueous suspension before it is subjected to step d), preferably has a solids content of from above 70 to 80 wt%, especially from 72 to 79 wt%, more preferably from 74 to 78 wt%, and most preferably from 76 to 78 wt% based on the total weight of the suspension.
• a grinding step which may be performed in any of the known grinding equipment with which those skilled in the art are familiar for grinding mineral materials. ' Especially conventional attritor mills such as those distributed by the company
• Dynomill are suitable in this respect, preferably using grinding balls made of glass, porcelain, and/or metal; especially preferably, however, grinding balls are used made of, e.g., zirconium silicate, zirconium dioxide and/or baddeleite with a diameter of 0.2 to 5 mm, preferably 0.2 to 2 mm, but also 0.5 to 5 mm, e.g., 1 to 2 mm. Quartz sand having an equivalent spherical diameter of 0.1 to 2 mm may also be used.
• At least one dispersing agent which preferably also act as a defiocculation agent, is added to the aqueous suspension of step b), wherein, the at least one dispersing agent may be completely added before grinding step c), or stepwise before and during grinding step c), and optionally also before and during and/or after grinding step c).
• Useful amounts of such dispersing agents added to the aqueous suspension during step b), during and after step b), but before step c), are from 0.01 to 1.25 wt%, preferably from 0.01 to 0.1 wt%, more preferably from 0.02 to 0.07 wt%, most preferably from 0.03 to 0.05 wt% based on the dry weight of the mineral material.
• Preferred amounts of such de-flocculation agents additionally added during step c) are from 0.05 to 1 wt%, more preferably from 0.1 to 0.7 wt%, even more preferably from 0.15 to 0.55, e.g. 0.3 wt% based on the dry weight of the mineral material.
• the total amount of the at least one dispersing agent added before grinding step c), or before and during step c), or before and during and/or after grinding step c), preferably is from about 0.01 to 1.25 wt%, more preferably 0.05 to 1 wt%, even more preferably 0.1 to 0.7 wt%, most preferably 0.3 to 0.5 wt% based on the dry weight of the mineral material.
• the dispersing agent is added in an amount such that, with respect to the specific surface area, measured by BET, of the ground material after step c), it is present in amount of below 0.15 rag/m , e.g. 0.05 to 0.08 mg/m 2 , if it is added before grinding step c), and, in an amount of from 0.05 mg/m 2
• Dispersing agents which may be used with respect to step b) and c) may be those selected from the group comprising homopolymers or copolymers of polycarboxylic acids such as acrylic or methacrylic acids or maleic acid; and/or their salts, e.g.
• the molecular weight Mw of such products is preferably in the range of from 1000 to 15000 g/mol, more preferably in the range of from 3000 to 7000 g mol, e.g. 3500 g/mol, most preferably in the range of from 4000 to 6000 g/mol, e.g. 5500 g/mol.
• At least one earth alkali oxide and/or hydroxide preferably lime and/or burnt dolomite is added to the aqueous suspension of step b), wherein lime in the context of the present invention comprises calcium oxide and calcium hydroxide.
• earth alkali oxide and/or hydroxide are sufficient to be used during grinding, such as amounts of from about 0.001 to 0.1 wt%, preferably 0.005 to 0.07 wt%, more preferably 0.007 to 0.05 wt%, most preferably 0.01 to 0.03 wt%, e.g. 0.02 wt% based on the dry weight of the mineral material.
• Grinding step c) may be carried out once or several times.
• the aqueous suspension may be partially ground in a grinder, the suspension of partially ground mineral material may then be fed to a second grinder for further grinding, etc., until the desired particle size is obtained.
• the desired particle size can also be obtained in one step by adjusting the residence time in the grinder. It is possible to grind the mineral material such that from 20 to 70 wt%, preferably from 36 to 68 wt%, more preferably from 40 to 60 wt%, e.g. 50 wt% of the at least one mineral material particles have a particle size of ⁇ 2 ⁇ after step c).
• the mineral material may be ground such that from 10 to 90 wt%, preferably from 20 to 80 wt%, more preferably from 36 to 75 wt%, especially from 40 to 70 wt%, most preferably from 50 to 65 wt%, e.g. 55 t% of the at least one mineral material particles have a particle size of ⁇ 1 ⁇ after step c),
• the aqueous suspension of ground mineral material may also be subjected to a separation step after grinding, wherein a finer fraction is separated from a coarser fraction, just as desired within the above-mentioned equivalent spherical diameter ranges of the mineral material.
• the separation may take place by means of well-known techniques such as screening, filtration, or centrifugation, wherein for the most applications
• centrifugation will be preferred, using commonly known equipment.
• step d the aqueous suspension of the ground, and optionally separated, mineral material is concentrated by flash cooling. Flash cooling in the context of the present invention is carried out by allowing water to evaporate from the aqueous suspension under the action of heat contained in the suspension.
• the temperature of the suspension may rise to the boiling point of the aqueous phase of the suspension, and the evaporation of water occurs naturally under the action of the heat contained in the suspension.
• the temperature generated by grinding may also be below the boiling point of the water contained in the suspension.
• the heat contained in the suspension as a result of the energy dissipated in the suspension during grinding may be sufficient to increase the percentage by weight of dry alkaline earth metal compound in the suspension to within the range from 79 to 85 wt% as mentioned below.
• the suspension may be heated by a heating means such as a heat exchanger to a temperature within the range of from 50 °C to the boiling point of the suspension, preferably to within the range of from 60 to 90 °C, more preferably from 70 to 85 °C, e.g. from 81 to 83 °C.
• a heating means such as a heat exchanger to a temperature within the range of from 50 °C to the boiling point of the suspension, preferably to within the range of from 60 to 90 °C, more preferably from 70 to 85 °C, e.g. from 81 to 83 °C.
• heat may be supplied to the suspension by passing the suspension through one side of a non-contact heat exchanger through the other side of which is passed a hot fluid, preferably at a temperature in the range from 50 to 100 °C.
• known flash cooler systems consist of a (vacuum) chamber, into which the suspension is fed. Depending upon the temperature and the vacuum, the water in the suspension will evaporate. The evaporation results in an increase of the solids content. Cooling will take place simultaneously.
• the temperature of the aqueous suspension at the inlet of the grinder may be from 20 to 80°C, preferably from 20 - 50°C, and at the outlet of the grinder, preferably of from 80 to 105 °C.
• the temperature of the aqueous suspension at the inlet of the flash cooler may be from 70 to 105°C, e.g. 95°C and at the outlet of the flash cooler less than 60 to 30°C, e.g. 35°C.
• the aqueous suspension is exposed to reduced pressure, preferably to a pressure of from 200 to 500 mbar, more preferably of from 250 to 400 mbar, most preferably a pressure of from 288 to 360 mbar, e.g. of from 300 to 350 mbar.
• the final solids content of the aqueous suspension obtained after step d) preferably is from 79 to 85 wt%, especially from 79.5 to 84 wt%, more preferably from 80 to 83 wt%, e.g. 82 wt%.
• the final solids content of the aqueous suspension after step d) is at least 1 wt%, preferably at least 2 wt%, more preferably at least 3 wt% higher than the initial solids content of the aqueous suspension obtained in step b).
• the initial solids content of an aqueous suspension of mineral material of 76 to 78 wt% is raised to 80 to 81 wt% by the process of the present invention, wherein the mineral material preferably is comminuted such that while initially 66 wt% of the mineral material particles have an equivalent spherical diameter of ⁇ 10 ⁇ , 36 to 65 wt% of the final mineral material produced according to the process of the present invention have an equivalent spherical diameter of ⁇ 2 ⁇ , and preferably even ⁇ 1 ⁇ .
• the Brookfield viscosity of the final aqueous suspension after step d) measured at 23 °C after 1 minute of stirring by the use of a RVT model BrookfieldTM viscosimeter at room temperature and a rotation speed of 100 rpm with the appropriate spindle is from 50 to 1000 mPa-s, preferably 100 to 750 mPa-s, more preferably from 150 to 600 mPa-s, most preferably from 200 to 460 mPa-s, e.g. 300 mPa-s.
• a second aspect of the present invention is the provision of a high solids aqueous suspension of mineral material(s) obtained by the process as described above.
• a high solids aqueous suspension of mineral material obtained by the process of the present invention especially preferably has a solids content of from 80 to 81 wt%, wherein 36 to 65 wt% of the mineral material have an equivalent spherical diameter of ⁇ 2 ⁇ , and preferably even ⁇ 1 ⁇ .
• a third aspect of the present invention is the use of the high solids aqueous suspension of mineral materials obtained by the process as described above in paper, paper coating colours, paints and plastics.
• the following examples and experiments serve to illustrate the present invention and should not restrict it in any way.
• the ground calcium carbonate suspension was continuously centrifuged in a conventional continuous centrifuge at a speed of 1200 rpm.
• the centrifuged aqueous suspension having a solids content of 76 wt% was fed into a continuously running flash cooler.
• the feeding speed was adjusted to reach approximately 80 wt% slurry solids at the outlet and concentrated at the following conditions:
• the final solids content after the concentration step was determined to be 80 wt% by drying 20 g of the suspension in an oven at 110 °C to weight constancy ⁇ 0.1 wt%.
• the Brookfield viscosity of the final aqueous suspension measured after 1 minute of stirring by the use of a RVT model BrookfieldTM viscosimeter at room temperature and a rotation speed of 100 rpm with a spindle No. 3 at the exit of the flash cooler was 150 mPa-s; 153 mPa-s after 24 hours, and 162 mPa-s after 3 days.
• the specific surface area of the dry calcium carbonate, measured by BET, was 12.5 mVg.
• the ground calcium carbonate suspension was continuously centrifuged in a conventional continuous centrifuge at a speed of 1300 rpm.
• the centrifuged aqueous suspension having a solids content of 78 wt% was fed into a continuously running flash cooler.
• the feeding speed was adjusted to reach approximately 80 wt% slurry solids at the outlet and concentrated at the following conditions:
• the final solids content after the concentration step was determined to be 80 wt% by drying 20 g of the suspension in an oven at 110 °C to weight constancy ⁇ 0.1 wt%.
• the Brookfield viscosity of the final aqueous suspension measured after 1 minute of stirring by the use of a RVT model BrookfieldTM viscosimeter at room temperature and a rotation speed of 100 rpm with a spindle No. 3 at the exit of the flash cooler was 460 mPa-s; and 575 mPa-s after 6 days.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
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• Medicinal Chemistry (AREA)
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• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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