EP0403473A1

EP0403473A1 - Process for preparing monodisperse titania spheres

Info

Publication number: EP0403473A1
Application number: EP19880903035
Authority: EP
Inventors: William L. Olson; William E. Liss
Original assignee: AlliedSignal Inc
Current assignee: Honeywell International Inc
Priority date: 1988-03-03
Filing date: 1988-03-03
Publication date: 1990-12-27
Also published as: WO1989008078A1; JPH03503045A

Abstract

Cette invention concerne un procédé permettant de former de manière reproductible des sphères en dioxyde de titane monodispersées par l'hydrolyse d'alkoxydes de titane, en présence d'un additif de régulation de taille contenant des amines, de manière à limiter la taille des particules dans une plage de tailles étroite.This invention relates to a process for reproducibly forming monodispersed titanium dioxide spheres by the hydrolysis of titanium alkoxides, in the presence of a size control additive containing amines, so as to limit the size of the particles. within a narrow size range.

Description

PROCESS FOR PREPARING MONODISPERSE TITANIA SPHERES

FIELD OF THE INVENTION

This invention relates to a method of preparing onosized or monodispersed titania spheres as particles by so-gel chemistry using a size control additive to produce excellent yields of the desired material. This invention relates, more specifically, to a process for reproducibly forming monodisperse titania spheres by the hydrolysis of titanium alkoxides in the presence of an amine-containing size control additive in such a way as to constrain the particle size within a narrow range.

BACKGROUND OF THE INVENTION

Ceramic materials offer a wide variety of possible physicochemical characteristics which are controlled by the inherent atomic structure and microstructure of the material. Their refractory nature and chemical inertness allow for the use of these materials in environments where conventional materials such as polymers do not survive. Although the potential for growth in new application areas is very strong, their use is actually limited by processing technology which cannot adequately meet the purity, strength, homogeneity, and microstructure requirements of high performance ceramic applications.

It'has been estimated that for a typical process which manufactures a high value added ceramic product, the cost of rejecting materials which do not meet specifications is generally in the range of 25 to 75% of the total manufacturing cost for a particular item. These numbers, which reflect processes which use conventional ceramic powders and processing technology, are clearly unacceptable and provide much of the stimulus for the resurgence of interest in the development of new or improved ceramic raw materials based on sol-gel and polymeric precursor chemistry.

Many of the current limitations to the use of ceramics in the high technology areas are a direct consequence of the physicochemical properties of the powders used in their fabrication. The raw material powder's average particle size, particle size distribution, agglomerate levels, and dispersion characteristics combine to limit the macroscopic homogeneity in the ceramic's green and final sintered state. The microstructural homogeneity of the ceramic can be optimized by processing powders where these characteristics are tightly controlled. Monodisperse metal oxide powders derived by sol-gel processes are prime examples of materials in-this form.

Monodisperse metal oxide powders offer many processing advantages over conventional ceramic powders. The spherical shape and narrow particle size distribution of the monodispersed powders allow for a tight control over the packing of the. owder particles in the green ceramic. Since there are very few agglomerates, the particles pack very uniformly with the residual pore sizes in the green ceramic often being on the order of two particle diameters (<1 micron) . If dispersions of the powder are slowly settled, very high green densities are attainable due to the statistical ordering of the particles with the residual pore size often on the order of one particle diameter. This is a crucial advantage since residual porosity or agglomerates on the order of a micron (or greater) in size in a fired structural ceramic can act as sources of cracks or defects in the material and lower its overall performance and strength. In processing conventional ceramic powders, the elimination of residual porosity and flaws resulting from poor powder packing and agglomerates is very difficult. This is typically accomplished by application of pressure during densification of the ceramic and by the addition of sintering aids to control grain growth. The application of pressure during high temperature processing is extremely costly and therefore undesirable. Additions such as sintering aids can adversely affect the high temperature properties of the material and therefore are also undesirable. With monosize powders, such processing steps are not necessary to achieve good densities, microstructural uniformity, and sinterability.

In addition to ensuring a more homogeneous green microstructure, monodisperse powders possess special advantages over conventional powders during the firing of the ceramic. Since the sintering temperature is inversely related to the size of the particles, the sub icron diameter of the powder particles results in lowering, often by several hundred degrees, the temperature required for sintering the material. The tightly controlled particle size eliminates the problems of differential sintering that can occur in conventional powders where the very small particles begin to sinter ahead of the larger particles in the compact. This process, which often results in undesirably large grain growth and grain size distributions and porosity, can have disasterous consequences for the performance and properties of the ceramic material. For monosize powders, sintering of the powder particles is rapid and spatially uniform and results in a homogeneous fine grained microstructure in the sintered article. Being a sol-gel derived material, sintering aids, if required, can be included in the powder cheaply and uniformly during the synthesis stage and the composition of the powder can be tightly controlled during processing. These onosized powders offer a unique opportunity for controlling many of the processing variables which now limit the performance and utilization of ceramic products.

Studies have shown that aging of the metal oxide powders can have a profound effect on the surface area and microporosity of the powder. Through appropriate control over the fabrication procedure it should be possible to develop powders and substrates with controlled micro and macroporosity highly useful as adsorbents, gas membrane and biological support materials, scanning electron microscope (SEM) calibrants, high strength structural ceramics and substrates. Presently, titania is used extensively in the construction of oxygen sensors, electronic components, and pigments. U.S. Patent 4,543,341 reported a route to monodisperse powders by a sol gel route. This work generated a great amount of excitement due to the resurgence of interest in sol gel chemistry and the large number of advantages these materials possess with respect to conventionally formed ceramic powders. In this prior work, a synthetic procedure for producing monodisperse silica from alkoxides was modified and extended to titania and zirconia.

U.S. Patent 4,543,341 also described the synthesis and characterization of a monodisperse, submicron titania powder possessing a spherical shape, uniform dimensions and low state of aggregation. The powder was prepared by mixing equal volume ethanol solutions of titanium tetraethoxide and water and stirring briefly. It was noted that powder isolation procedures must be initiated within thirty minutes of the onset of precipitation, or hard necked aggregates of the individual powder particles would form. Isolation procedures consisted of centrifuging the freshly prepared powder at low speed followed by decantation of the sol. The powder was washed with ethanol followed by washing with alkaline water to impart a negative charge to the titania particle's surface thereby providing a net repulsive interparticle potential which inhibits flocculation of the powders. BRIEF SUMMARY OF THE INVENTION

Accordingly, it is an object of this invention to furnish a process which can reproducibly produce monodisperse spheres of titania as a formed compact or as a dispersion in an appropriate liquid medium.

It is a further object of this invention to furnish spheres of titania with an individual particle size in a range of from about .1 to about 1 micron and with a standard deviation of the particle size distribution of about one-half of the average particle diameter, thereby defining the term monodisperse or monosize.

In one aspect an embodiment of this invention is found in a process for making monodisperse titania comprising the steps of: dissolving a titanium tetraalkoxide in a liquid comprising an alcohol to form a solution of said alkoxide; and thereafter adding an amine-containing size control additive and water to the solution to form a precipitate of solid monodisperse spheres of titania.

A further embodiment of the invention is found in a process for increasing the internal porosity of the monodisperse titania particles comprising the aging of dispersions of said titania in mediums such as basic water or titanium-alkoxide based sols.

A still further emdobiment of this invention is found in a process for producing green body compacts comprising the addition of a dispersion of said titania particles to a porous mold and the recovery therefrom of said solid green body compact. Other objects and embodiments will be found in the following further detailed description of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

This invention is concerned with the production of monodisperse titania particles from an alcoholic solution of titanium tetraalkoxide using an amine-containing addi- tive and water to hydrolyze said titanium alkoxide solution thereby producing the desired titania particles with subsequent separation and recovery of said monodisperse titania particles. In this manner, a solution of titanium tetraethoxide may be dissolved in ethanol, sec-butyl amine may be added, following which aqueous ethanol may be added to the resultant solution, to afford a precipitation of the desired monodisperse titania particles which can be separated from the solu¬ tion and recovered as spherical solids. If so desired, hydroxypropyl cellulose can be added to the alcohol when mixing with the alkoxide or with the water although it is preferred to be added to the alcohol-water mixture. In addition, the monodisperse titania particles may be redispersed in a redispersing medium and recovered as a dispersion of said titania particles.

The redispersal of the monodisperse titania powder can be effected in any manner known to a person skilled in the arts though it is preferable to redisperse using a high frequency sonication device such as, for example, Vibra Cell made by Sonics Materials, and to utilize a dispersing medium chosen from the group including, but not limited to, ketones, alcohols of from one to four carbon atoms, aldehydes, water, chlorinated hydrocarbons, carboxylic acids, and amides. Depending on the dispersion medium that was chosen and the weight percent loading of the powder in said medium, the redispersed material can be used in a variety of ways. The redispersed material can then be charged into a porous mold and a compact, green body ceramic formed, the material can be cast in the form of a tape, settled slowly into a uniformly packed green ceramic, or the material can be aged from 1 day to 14 days in a medium such as basic water with a pH range of from about 8 to about 11 wherein the preferable base is ammonium hydroxide. The aging conditions include a temperature from 15°C to about 90°C and a pressure in the range of from about 1 to about 10 at and result in a recovered product with a surface area increase that is in a range of from about 100 m /g to about 300 m²/g. For instance, the typical unaged product has a surface area of about 5 m²/g and the aging process increases the surface area to about 200 m²/g.

The titanium tetraalkoxide used in this invention, having a formula Ti(OR)₄ wherein R represents a lower alkyl group of from one to four carbon atoms, can be selected from the group including, but not limited to, titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, titanium tetrasecbutoxide; titanium tetraisopropoxide, titanium ethoxytriethoxide, titanium ethoxypropoxydibutoxide, titanium dimethoxydiethoxide and titanium methoxyethoxypropoxybutoxide.

The alcohol (ROH) used in this invention can be selected from the group including, but not limited to, methanol, ethanol, 1-propanol, 1-butanol, 2-propanol, 2- butanol, 2-methyl-2-propanol. It is important to realize that the alcohol, of formula ROH, can have its R group selected from lower alkyl groups of from one to four carbon atoms.

In the preparation of this invention, it is preferred that the titanium tetraalkoxide is present in the alcohol solution at a concentration in the range of from 0.05 M to 1.0 M.

It is important to realize that the water content of the final hydrolysis mixture should not exceed a molarity of water in the range of from .2 M to 1.5 M and that the starting alcohol solution should have no more water than 500 parts per million (ppm) with a preferable level of 200 ppm. Additionally, the water content of the titanium tetraalkoxide alcohol is preferably in a range of from 100 ppm to 300 ppm.

This invention concerns new size control additive systems which produce onosized titania by sol gel chemistry. Sec-butyl amine and triethyl amine/hydroxypropylcellulose are two such preferred additive systems that are capable of preventing flocculation of the powder particles during precipitation/formation and of giving monodisperse spherical powders directly upon hydrolysis of the titanium alkoxide. These additives represent a significant advance beyond the described prior art since they provide a method by which highly uniform dispersions of monosize titania particles can be produced in a very reproducible manner. Typically, the additive is used in an amount sufficient to result in the solution containing from 0.001 M to 0.1 M.

In the broadest embodiment, amines with alkyl groups of from 1 to 7 carbon atoms in length may be employed to effect the process of this invention. The best results may be obtained for mono- and di-substituted amines when used in the absence of hydroxypropylcellulose (HPC) whereas the best results may be obtained for trialkyla ines in the presence of HPC. It is also within the scope of this invention to use mixtures of amines as well as individual amines.

The mono- and di-substituted amines for use in this invention can be selected from the group including, though not limited to, ethylamine, diethylamine. methylamine, dimethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexyla ine, heptylamine, diheptylamine, isopropyla ine, diisopropylamine, isobutylamine, diiosobutylamine, sec-butylamine, disec-butylamine, tert- butylamine, ditert-butylamine, isopentylamine, tert- heptylamine, ethylpropylamine, hexylbutylamine, etc.

Trialkyl amines for use in this invention can be selected from the group including, but not limited to, triethyla ine. trimethylamine, triisopropylamine, tributyla ine, triisobutylamine, tri-sec-butylamine, tri- tert-butylamine, tripentylamine, triisopentylamine, trihexylamine, triheptyla ine, methyldiethylamine, ethylmethylpropylamine, propyldiethylamine, hexylmethylpentylamine, propylethylheptylamine, pentyldibutylamine, etc.

For purposes of this specification and in the appended claims, the terms monodisperse and monosize will be used interchangeably and mean that the particle size distribution is such that the standard deviation of the particle size distribution is less than one-half of the average particle diameter.

In a preferred embodiment, the concentration of sec- butylamine is to be in a range of from about .001 M to about .1 M, the concentration of triethylamine to be in the range of from about 0.001 M to about 0.1 M, and the concentration of hydroxypropylcellulose to be in the range of from about 0.5 to 5 weight percent based on alkoxide. Alternatively, the amine such as triethylamine may be present in an amount in the range of about 1 to about 6 mole percent based on titanium metal.

These amine additives, in addition to controlling the relative sphericity of the powder particles, are - extremely effective in controlling the average particle size of the precipitated powder. Simply changing the concentration of an amine containing additive may result in an increase or decrease in the average size of the titania particles, while still preserving the narrow size distribution of the powder. This size change is achieved while keeping both the water and alkoxide reagent concentrations (as well as other reaction conditions) constant and represents a fundamental advance in the production of these materials.

While it is clear that size control additives are critical to the success of the reaction schemes described within, their role in the process is not clear. Unlike organic polymerization reactions which are well defined, the inorganic polymerization chemistry of metal alkoxides is very complex. The structures of many of the metal alkoxides are not explicitly known, since they exist as mixtures of oligomers in solution. The ratios between the various oligomers present in the solution are expected to be affected by factors such as distillation, the presence of other Lewis bases such as alcohols or amines, and the manufacturing procedures used in their synthesis. The presence of small quantities of water will also affect not only the molecular structure and composition of the metal alkoxide oligomers, but the relative hydrolysis rates of those compounds. What results from this gigantic matrix of variables is an extremely complex chemical system which constitutes the starting material for the synthesis of monodisperse metal oxide powders. Thus the development of additive systems such as those described herein permit the reproducible synthesis of monodisperse titania powders from such complex starting materials.

The synthesis of monodisperse powders by sol gel techniques requires that several critical criteria be met during the nucleation and growth stages of particle formation. One of the most critical elements in this process is the homogeneity of the solution. In order to form a monodisperse powder by solution precipitation techniques, homogeneous nucleation and growth of the particles must occur, thus requiring that possible nucleation sites be removed from the solvent prior to precipitation. Such removal is commonly achieved by filtering the reagent solutions through a submicron filter (Millipore) , thereby effectively removing any dust or fine precipitates which could act as nucleation sites and give rise to a nonuniform rate of nucleation and growth of the metal oxide particles.

It is also important, particularly for hydrolysis reactions of metal alkoxides, that the hydrolysis reactions proceed at a rate sufficient to assure the rapid growth and precipitation of the material, yet not too rapid that precipitation occurs immediately upon reagent addition. If the reaction is extremely rapid, local areas of supersaturation develop in the sol with the concomitant formation of non-uniform precipitates. Thus the solution must be uniform with no local supersaturation, and particle growth must proceed at an appreciable rate following the initial precipitation.

Another aspect which must be incorporated into any successful reaction scheme is to stabilize the particles during their growth in the sol, a very critical factor in the nonreproducibility of the reaction chemistry for titania. During the early growth stages of the particle, the particle's surface must be sufficiently charged, or otherwise sterically stabilized such that interparticle forces are of a repulsive nature and provide a barrier to hard aggregate formation. For powders which are synthesized in pH conditions close to the zeta potential of the metal oxide, "agglomeration" processes (flocculation followed by precipitation of material on the flocculated particle clusters) are certain to occur in concentrated dispersions of the powders, unless they have been stabilized in some manner. This is the major problem which needed to be resolved in order to reproducibly synthesize monodisperse titania powders from alkoxides. The process of this invention can be effected in a batch manner whereby the titanium tetraalkoxide is mixed with the alcohol in a suitable vessel, followed by subsequent addition of the amine containing additive and the aqueous alcohol medium. After a suitable period of mixing, the resultant solid monodisperse titania particles are separated from the reaction mixture, washed with a suitable washing medium, and recovered as solid particles.

The separation and recovery of the monodispersed titania particles can be carried out by any means known to those skilled in the art, including such means as gravity settling, batch or continuous centrifugation, and filtration. Precipitation times in the range of from about .1 to about 30 minutes are preferred.

The redispersing medium can be selected from the group including, but not limited to, ketones, water, alcohols of from one to four carbon atoms, aldehydes, chlorinated hydrocarbons, carboxylic acids, amines, and solutions of acids or bases.

Prior to the final separation of the monodisperse powder body from the liquid, the reaction liquid can be separated and the body can be washed several times with a liquid taken from the group including, but not limited to, water and alcohols of from one to four carbon atoms.

Alternatively, the precipitation reaction may be effected in a continuous manner of operation. When this type of operation is employed, a quantity of solution A, comprising titanium tetraalkoxide, ethanol and the amine additive, is continuously prepared from its constituent reagents and charged into a quantity of solution B, comprising water and ethanol, which has been placed in a suitable vessel maintained at the proper operating conditions of temperature and pressure. After a suitable time of mixing in the reactor, effluent is continuously withdrawn and subjected to conventional means of separation whereby the desired titania powder is recovered, and the withdrawn stream can be recycled, if so desired. The recovered titania can be redispersed as in the batch reaction or recovered as a solid product.

The monodisperse titania particles are produced in a relatively narrow range of particle size corresponding to a standard deviation of the particle size distribution of less than one-half of the average particle diameter whereas the prior work produced particle size markedly exceeding 1 micron, poor uniformity, with standard deviations no less than the average particle diameter. The present invention produces spherical uniform particles in a particle size range of from about .1 to about l.0 micron in contradistinction to the prior work where experiments produce particle sizes in excess of 1 micron. The well defined, spherical shape and narrow range of particle size, which is obtainable when employing the process of the present invention, fulfills a long felt need in the ceramic industry for a powder capable of forming high density, microstructurally uniform, green body compacts.

In contradistinction to the published literature, the titania particles which are obtained from processes known in the literature are not reproducible and that the product of said known processes was found by scanning electron microscopy (SEM) to be highly agglomerated with an average particle size of 1.2 microns as determined by the Leeds and Northrup small particle analyzer (SPA) . The prior work reported a particle size of 0.3-0.7 microns whereas, despite extensive and exhaustive attempted replication of this work, the disclosed procedure produced resultant particles which were hard, necked inseparable aggregates with a 1.2 micron size and made up of approximately spherical .3 micron particles of titania. For purposes of this specification and in the appended claims the term "compact" will be defined to include both the separated, non-redispersed titania as well as the formed solid titania resulting from the action of a porous mold on the dispersion of monodisperse titania, or by other forming procedures known to a person skilled in the art. Additionally the term "green body" will be defined to mean an unfired, preceramic compact. The following examples are given for purposes of illustration. However, it is to be understood that these examples are only illustrative in nature and that this invention is not necessarily limited thereto.

CONTROL EXAMPLE I

In order to differentiate this invention from prior work, products were made utilizing procedures described in the literature. The titanium tetraethoxide was obtained from three different manufacturers, was purified by vacuum distillation, and carefully handled under an inert nitrogen atmosphere to insure that exposure to atmospheric moisture was kept to a minimum. All of the reaction solutions were filtered through a 0.4 micron

Millipore filter (nylon) just prior to their use. All of the solution handling operations were carried out under a dry, inert atmosphere of nitrogen.

The particle size distribution values were obtained on a Leeds and Northrup Small Particle Analyzer (SPA) . This instrument measures the particle size distributions over a range of 0.1-35 microns by laser light scattering. A scanning electron microscope (SEM) was used to check the SPA-determined particle size values and to examine the morphology of the powder particles. Excellent agreement was always obtained between the SEM and SPA size data providing that proper precautions were taken to insure that proper powder sampling procedures were followed. Following the known reported procedure, a dilute, 0.2 molar (M) solution of titanium tetraethoxide in anhydrous ethanol was added to a solution of water in ethanol [0.83 M] to give a precipitation time for this experiment of about 10 seconds. After thirty minutes, The resultant powder was washed with ethanol, redispersed in a pH 10 solution of deionized water, and the particle size was determined by SPA. The average SPA particle size of 1.3 microns is several times greater than that claimed in the prior work for this material. An SEM micrograph of the powder clearly shows the particle surfaces to be curved or spherical with most of the particles in the 0.3 micron size range present in hard necked aggregates.

In addition, the surface at 30,000 magnification appears to be fairly smooth, exhibiting very little microstructure. Although the particle size is not correct, the surface appearance of the powder closely matches the description of the powder reported for this material. This observation is important since the powders prepared utilizing a variety of different additives have surface microstructures markedly different from those of the prior work. The precipitation times observed for comparable reagent concentrations were very close to the literature values. In general, a decrease in either the water or alkoxide concentrations resulted in a longer precipitation time, but the key product discrepancies entailed the morphologies and sizes of the powder particles. The material obtained upon duplication of the prior procedures consistently gave non-uniform, agglomerated powders with average particle diameters of over one micron as determined by SPA and independently verified by SEM.

A large number of alternate reagent concentrations, reaction temperatures, and experimental conditions were examined. The particle size and microstructure of the titania powders prepared by these procedures were remarkably invariant to changes in the processing conditions. These changes included utilizing titanium ethoxide in the reactions in its as-received, first distilled and second fraction distilled forms, along with the 200 proof anhydrous ethanol. Reactions were run using deionized water (18 megohm) and distilled water.

In addition to these precautions, careful attention was given to solution handling, powder washing, isolation, and redispersion procedures following powder precipitation. Precipitation reactions were run statically, or with slow or vigorous stirring, and centrifugation rates were varied as were the sonication power and solvents used to redisperse the powders. The results of over 40 experiments utilizing processes found in prior publications disclosed the fact that the particles which were obtained did not reproduce the claimed results.

CONTROL EXAMPLE II

This example was performed to show the effect of triethylamine without HPC on the reported experimental procedures. A [0.2 M] solution of the alkoxide containing 2 mole percent of triethylamine (based on Ti) was prepared and mixed with a 0.83 M solution of water in ethanol as described as in Example I. With this incorporation, the precipitation time of the solid titania increased from 10 seconds to 35 seconds and the powder precipitated from the sol in a highly flocculated state exhibiting an average particle size of 10.4 microns. Upon redispersing the isolated powder sample in pH 10 water, the average SPA particle size of the powder was reduced to 1.1 micron, a value very comparable to that obtained for the unmodified synthesis (1.06 micron) as carried out in Example I.

The laser light scattering and SEM characterization results of the experiments with triethylamine clearly showed that the freshly precipitated powders were highly agglomerated and even upon redispersion in basic water failed to produce a material with an average particle size ^.ess than 0.9 microns. Despite purifying the amine by distillation from barium oxide, the powder which was produced using the distilled amine, exhibited a similar particle size distribution, to that obtained using the undistilled material. EXAMPLE I

In order to observe the effect of a primary amine additive, an alkoxide solution (A) was prepared by mixing 4mL of freshly distilled titanium tetraethoxide (Ti(0Et)₄), 10 microliters of sec-butyl amine and 100 mL of dry ethanol together under an inert atmosphere of dry nitrogen. The hydrolysis solution (B) was prepared by adding 3mL of distilled water to lOOmL of absolute ethanol. Both solutions were then individually filtered through a 0.4 micron Millipore nylon filter under nitrogen to remove fine particulates from the solutions. The hydrolysis was carried out by taking equal volume portions of both solutions and mixing them vigorously for several seconds, after which the well-mixed solution was allowed to remain undisturbed for 30 minutes. The initially transparent solution became turbid 13 seconds after mixing. The resulting milky dispersion of titania powder was centrifuged for 20 minutes, the ethanol was decanted from the powder compacts, and the powder was ultrasonically dispersed in a small quantity of ethanol. The powder was then again isolated by centrifugation, redispersed in pH 10 water and the particle size distribution measured by light scattering using a Leeds and Northrup Small Particle Analyzer (SPA) . The average size of the titania particles was 0.88 microns. SEM micrographs of a dried portion of the powder dispersion independently confirmed the uniform, spherical particle morphology and particle size distribution of the precipitate.

CONTROL EXAMPLE III

This example was run as a control experiment in tandem with Example II utilizing the same stock solutions of water and alkoxide. Utilizing the basic method of Example I, a Millipore filtered solution of 4mL of freshly distilled Ti(0Et)₄ in lOO L absolute ethanol was added to a similarly filtered solution of 1.5 mL distilled water in lOOmL ethanol under an atmosphere of dry nitrogen. The resulting solution was swirled briefly and then allowed to remain undisturbed for twenty minutes. The initially transparent reaction solution became cloudy 28 seconds after mixing, and, after equilibrating for thirty minutes, the solution was examined visually. Large clumps of powder particles were seen in the sol and were clear evidence that flocculation had occurred. The average size of the precipitate measured by laser light scattering was 9.56 microns and in agreement with the visual observation of clumping. Attempts to reduce the average particle size of the precipitate by ultrasonically redispersing a centrifuged compact at high power in either ethanol or pH 10 water was only moderately successful. While the average size of the redispersed material was smaller, it was always greater than 1 micron in diameter. Examination of the powder by SEM revealed that the powder particles largely consisted of hard, necked aggregates of 0.3 micron titania particles. From the average SPA determined particle size of 1.3 microns, it is estimated from the SEM micrographs that the "average titania particle" in this sample consisted of an agglomerate of 3 or more 0.3 micron primary particles of titania.

EXAMPLE II

This example was run to show the effect of the amine addition of the invention to the Control Example III. To a solution of titanium ethoxide in ethanol prepared as in Control Example III was added 18 microliters of freshly distilled sec-butyl amine. This solution was filtered through a 0.45 micron Millipore filter and then added to a solution of 1.5 mL of distilled water in lOOmL ethanol. This reaction, run concurrently with the unmodified reaction described in the control became turbid 30 seconds after mixing of the solutions. The appearance of the dispersion, in contrast to that described above, had a very uniform (milky) appearance with no evidence of large precipitates being visually apparent. The average particle size of the dispersion measured by light scattering and independently confirmed by SEM measurements, was found to be 0.75 microns. In addition, the powder was found to have a spherical particle morphology by SEM.

EXAMPLE III

This example demonstrates the effect of increasing the concentration of the amine of the present invention. Using the method described in Example II, 4mL of distilled Ti(OEt)₄ was dissolved in 100 mL of absolute ethanol and 57 microliters of sec-butyl amine was added to form Solution A. After filtering through a Millipore filter. Solution A was mixed with filtered Solution B, comprising 1.5 L of water in 100 mL absolute ethanol. The resulting solution became turbid in 55 seconds. The average particle size of the precipitated titania particles was 0.47 microns and was highly uniform in size and particle morphology. In comparison with Examples I and II above, it can be seen that an increase in sec- butyl amine in Solution A produced an reduction in size of the titania particles from 0.88 microns in Example I to 0.75 microns in Example II to 0.47 microns in the present example as shown in Table I below:

TABLE I

TITANIA PARTICLE SIZE

EXAMPLE Sec-butyl Amine Particle Size I 10 microliters 0.88 microns II 18 microliters 0.75 microns

IIII 57 microliters 0.47 microns CONTROL EXAMPLE IV

A solution of 8 L of titanium tetraethoxide (Ti(0Et)₄) in 200 L of absolute ethanol was prepared and filtered as in Example IV and then mixed with 0.27g of hydroxypropylcellulose (HPC) with vigorous shaking to form Solution A which was then added to Solution B, comprising 3 mL of water in 200 L of absolute ethanol. Turbidity appeared after 24 seconds. After a thirty minute equilibration, the solution was centrifuged to give a powder compact which was washed as before. The average particle size of the spherical titania precipitate was 0.21 microns.

EXAMPLE IV In like manner as in Control Example IV, except that Solution A now contained 106 microliters of triethyl amine. Solutions A and B were mixed and the resultant powder compact treated as before to give an average particle size of 0.59 microns for the highly spherical titania powder. A comparison of the results of these two examples shows that the addition of triethylamine, in accord with the present invention, to the HPC increased the average size of the titania powder from 0.21 microns to 0.59 microns while preserving the sphericity of the particles.

EXAMPLE V

. A series of reactions were run as described above in Example I in order to determine the effect of various types of amines on the hydrolysis chemistry of titanium ethoxide. In a typical reaction, 2mL of Ti(0Et)₄ was dissolved in 50 mL of ethanol with 3 mole percent of a particular amine (based on titanium) . This solution was filtered through a sub icron Millipore filter under nitrogen and then added to a solution of 0.75mL of water in 50mL of ethanol. The reaction solution, which was always initially transparent, was swirled rapidly to ensure good mixing and then allowed to remain undisturbed for 30 minutes. The onset of turbidity was found to be dependent on the identity of amine, ranging from 27 to 45 seconds. Small portions of the powders were removed and characterized by light scattering and SEM. The powder particles were found to be highly uniform spheres with a narrow size distribution. The results are summarized in Table 2 below:

TABLE I

ONSET OF PARTICLE

AMINE AMOUNT ADDED TURBIDITY SIZE

Isopropyl 25 microliters 45 sec 0.50

Diethyl 31 microliters 43 sec 0.50

Propyl 24 microliters 30 sec 0.87

Butyl 29 microliters 32 sec 0.75

Di-butyl 50 microliters 40 sec 0.44

Hexyl 39 microliters 2.7 sec 0.62 sec-butyl 28 microliters 45 sec 0.71

Claims

CLAIMS :

1. A process for making monodisperse titania spheres comprising the steps of a) dissolving titanium tetraalkoxide in a liquid comprising an alcohol to form a solution of said alkoxide; and thereafter b) adding an amine-containing size control additive and water to the resulting solution to form a precipitate of solid monodisperse spheres of titania.

2. The process as set forth in Claim 1 further characterized in that said alcohol has the formula ROH in which R represents lower alkyl groups of from one to four carbon atoms.

3. The process as set forth in Claim 1 or 2 further characterized in that said titanium tetraalkoxide is present in said solution at a concentration in the range of from .0.05 M to 1.0 M.

4. The process as set forth in Claim 1, 2 or 3 further characterized in that said alcohol is selected from the group consisting of ethanol, methanol, 1- butanol, 1-propanol, 2-propanol, 2-butanol, and 2-methyl- 2-propanol.

5. The process as set forth in any one of Claims 1 to 4 further characterized in that said amine-containing size control additive comprises an amine selected from the group consisting of isopropylamine, diethylamine, propyl- amine, butylamine, sec-butylamine, di-butylamine, hexyl- amine and mixtures thereof.

6. The process as set forth in any one of Claims 1 to 5 further characterized in that said additive is present in the solution in the range of from 0.001 M to 0.1 M.

7. The process as set forth in any one of Claims 1 to 6 further characterized in that said additive is a mixture comprising triethylamine and hydroxypropylcellulose.

8. The process as set forth in Claim 7 further characterized in that the triethylamine is added to the solution in an amount of 1 to 6 mole percent, based on titanium, and in that the hydroxypropylcellulose is added to the solution in an amount corresponding to 0.5 to 5 weight percent based on the titanium tetraalkoxide.