LOW DENSITY SILICA PARTICLES AND METHOD FOR THEIR PREPARATION

Abstract: Internal porosity is created in dense SiO2 particles by heating a mixture of the particles with B2O3 at a temperature above about 450 DEG C. Resulting SiO2 particles have altered morphology, internal porosity, and small to negative volume changes when heated.

Description: TITLE LOW DENSITY SILICA PARTICLES AND METHOD FOR THEIR PREPARATION CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of Application Serial No. 08/871,162 filed June 9, 1997. BACKGROUND OF THE INVENTION Technical Field This invention relates to low density silica particles conveniently prepared by heating a mixture of boric acid or B 2 O 3 with silica particles at a temperature above about 450°C. Silica particles so prepared individually have internal porosity and exhibit unique properties, such as a small to negative thermal expansion coefficient when first heated after preparation. The particles are useful for a variety of applications, such as a catalyst support or in resin blends used in electronic packaging. Background Information Silica particles are well known in the art and have found a broad range of applications due to the chemical inertness of silica and its favorable dielectric properties. Common applications include use as a catalyst support, as media in liquid chromatography, and as filler in resins employed in electronic packaging. Silica generally is prepared using a mechanical, fumed, or chemical process. Conventional mechanical processes produce solid particles having little or no internal porosity. Variations in bulk densities are attributed to particle size- and how tightly the particles are packed. Conventional fumed silicas are produced by high temperature (1800°C) hydrolysis of silicon tetrachloride. This process is expensive, produces corrosive hydrogen chloride as a by-product, and the product silica has an undesirable low bulk density. Conventional chemical processes for producing xerogels and aerogels do create particles having internal porosity, but these processes are even more expensive than those for fumed silicas, and there is limited commercial capacity. The lower cost mechanical processes tend to produce particles having an angular morphology that, are undesirable for applications such as resin/filler systems used in electronic packaging. Thus, there continues to be a need for economical methods of producing silica particles having internal porosity. Also, there continues to be a need for silica particles having unique properties. SUMMARY OF THE INVENTION It now has been found that internal porosity can be introduced to silica particles, and any surface angularity can be reduced, by heating the silica particles in the presence of B 2 O 3 to a temperature above about 450°C. Accordingly, the present invention provides a process for preparing silicon dioxide particles comprising, in sequence: a. forming an intimate mixture of silicon dioxide particles and at least one boron compound selected from the group consisting of B 2 O 3 and boric acid; b. heating said intimate mixture to a temperature above about 450°C for a time sufficient to alter the density and/or morphology of said individual silicon dioxide particles; c. cooling the mixture to ambient conditions; and d. recovering discrete silicon dioxide particles. It also has been discovered that the recovered silicon dioxide particles have unusual properties. For those recovered silicon dioxide particles heated to a temperature above about 450°C to about the temperature at the liquidus curve of the mixture, the particles have the property of having a low average volume change of about ±0.5% over the temperature range of 100-900°C. This property makes the particles particularly useful as filler to adjust the thermal expansion coefficient of resins applied during the fabrication of articles, such as electronic packaging, to minimize thermal induced stresses during the manufacture process. Accordingly, this invention also provides discrete porous SiO 2 particles that have a low average volume change of about ±0.5% over the temperature range of 100- 900°C. For those particles heated to a temperature above the liquidus curve of the mixture, the particles have the property of shrinking when subsequently heated to a temperature in the range of approximately 100° to 400°C. This property makes the particles particularly useful as catalyst supports and thickeners. Accordingly, this invention also provides discrete porous SiO 2 particles that have an Initial Negative Expansion Coefficient, as the term is defined herein. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a phase diagram for crystalline silica and B 2 O 3 . Figure 2 illustrates dimensional changes observed in pellets made from a lot of particles prepared in accordance with the invention by heating silica particles in the presence of B 2 O 3 to a temperature above the liquidus curve, upon a subsequent heating. Figure 3 illustrates dimensional changes observed in pellets made from a second lot of particles prepared in accordance with the invention by heating silica particles in the presence of B 2 O 3 to a temperature above the liquidus curve, upon a subsequent heating. Figures 4 through 7 illustrate dimensional changes observed in pellets made from commercial lots of particles upon heating. Figure 8 illustrates dimensional changes observed in pellets made from a second lot of particles prepared in accordance with the invention by heating silica particles in the presence of B 2 O 3 to a temperature of about 500°C, upon a subsequent heating. DESCRIPTION OF THE PREFERRED EMBODIMENTS The silica particles of the invention conveniently are prepared by forming a mixture of B 2 O 3 or boric acid (H 3 BO 3 ) with amorphous or crystalline silica particles and heating the mixture to a temperature above about 450°C as described in detail hereinbelow. The mixture then is cooled and the B 2 O 3 is removed. Silica particles thereby formed have internal porosity. Silica/Boron Mixture The selected silica may be amorphous or crystalline, such as fused silica or quartz. The effect of the invention is achieved with any size of silica particles, but the selected particles typically have any average particle size in the range of 5 to 500 microns. Typical starting materials include beach sand, quartz, or commercial fused silicas. The silica particles are blended with B 2 O 3 , boric acid, or other precursors that forms B 2 O 3 in situ, in dry form or preferably with the addition of water to facilitate formation of an intimate mixture. As used herein, the compound "B 2 O 3 " includes a precursor compound that breaks down in situ to form B 2 O 3 . Conventional mixing equipment is employed for this purpose. The effect of B 2 O 3 on the silica particles may be observed at low levels, such as with mixtures containing 5% B 2 O 3 by weight. Typically the mixture will contain 20% to 70% B 2 O 3 , preferably 30% to 60% B 2 O 3 , wherein the percentages are weight percentages of the total SiO 2 and B 2 O 3 mixture. If boric acid or another precursor of B 2 O 3 is selected, the quantity added is adjusted such that the actual quantity of B 2 O 3 is within the desired range. Selection of the optimum amount of B 2 O 3 varies with the SiO 2 particles selected for the process, heating "soak time" as discussed hereinafter, and the extent to which it is desired to introduce internal porosity to the particles. Another factor taken into account is the cost of processing and recovering B 2 O 3 in the process. Heating Step The blend of SiO 2 , B 2 O 3 and/or boric acid, and water (if introduced as a mixing aid) is heated to an elevated temperature. Any boric acid present decomposes to form B 2 O 3 and water, which rapidly evolves and is removed from the mixture along with any water present as a mixing aid. As illustrated in Figure 1, B 2 O 3 melts at approximately 450°C at all concentrations. The temperature at which crystalline SiO 2 (e.g., quartz and related tridymite and cristobalite) also melts, however, varies with the relative proportions of SiO 2 and B 2 O 3 contained in the mixture, as reported by T. J. Rockett and W. R. Foster in Journal of American Ceramic Societv. 48 [2], pages 75 to 80 (1965). The phase diagram for amorphous SiO 2 and B 2 O 3 is similar, with the amorphous silica melting at a temperature between about 450°C and 1600°C that varies with the relative proportions of SiO 2 and B 2 O 3 contained in the mixture. The term "liquidus curve" refers to the plot of composition- dependent temperatures at which the SiO 2 and B 2 O 3 are both in the liquid phase. In accordance with the invention, the mixture is heated to a temperature above about 450°C. It will be appreciated that the SiO 2 may not melt at this temperature, but there is a "soak time" during which the elevated temperature takes effect. The desired soak time will vary with the selected temperature, size and moφhology of the SiO 2 particles, and the extent to which it is desired to introduce internal porosity in the SiO 2 particles. Not much effect is observed at soak times as short as 30 minutes when a temperature is selected only slightly above 450°C. The selected soak time typically will be 1 to 20 hours, preferably 1 to 4 hours. The impact on the silica particles of treatment with B 2 O 3 begins at about 450°C and becomes more pronounced at temperatures above the liquidus curve. Depending on the desired properties in the product silicon dioxide particles, the - B 2 O 3 /SiO 2 mixture may be heated to temperatures above the liquidus curve for the particular mixture that has been selected. When the mixture is heated to temperatures above the liquidus curve, there is a similar "soak time" during which SiO 2 particles become liquid. It is not desirable to totally melt the SiO 2 particles. The selected soak time for temperatures above the liquidus curve is also typically 1 to 20 hours, and preferably 1 to 4 hours. It is important to note that, for the puφoses of the invention when the mixture is heated to a temperature above the liquidus curve, B 2 O 3 and SiO 2 behave as immiscible liquids at soak times and temperatures typically selected in practicing the invention. Cooling Step When the mixture has been held the selected elevated temperature for the selected soak time, it then is cooled to ambient temperature. This cooling step may be performed continuously or in stages. When the elevated temperature is above the liquidus curve, in one embodiment, cooling is performed in two stages. In the first stage, the mixture is cooled to a temperature above the melting temperature of B 2 O 3 , i. e., about 450°C, but below the liquidus curve temperature for that composition, and held within that temperature range for sufficient time to permit the SiO 2 to solidify as durable particles capable of withstanding physical processing. Typically hold times of 30 minutes to 2 hours are suitable for this puφose. This embodiment offers the potential advantage of permitting easier removal of the mixture from the heating vessel rather than waiting until the mixture has reached ambient temperature. In this embodiment, a portion of the B 2 O 3 (which is still in the liquid state) can be removed from the SiO 2 particles mechanically, such as by filtration. Similarly for mixtures which have been heated to temperatures above 450°C, yet below the liquidus curve, a portion of the B 2 O 3 which is in the liquid state, can also be mechanically removed from the silica particles. The portion containing the solid SiO 2 particles then is cooled to ambient temperature. Particle Recovery Residual B 2 O 3 contained in and on the SiO 2 particles is readily removed by washing with water. The compound B 2 O 3 generally is not considered environmentally hazardous, and boron compounds may be additives in commercial compositions employing the SiO 2 particles. Thus, it may not be necessary to take elaborate care to remove trace quantities of B 2 O 3 contained in internal pores of the SiO 2 particles for many applications. Particle Properties Resulting SiO 2 particles have a substantially higher surface area and substantially lower bulk density than the particles introduced to the process due to internal porosity formed in the particles. Bulk density of dry powder consisting of these particles typically is in the range of 0.2 to 0.9 g/cc, compared to the bulk density of 1.0 g/cc for a typical commercial fused silica powder. Surface areas of the powders range from 20 to over 400 m 2 /g. It should be recognized that physical properties of the products will depend on method of preparation including composition of the mixture, temperature to which the mixture is heated and soak time. Individual particles typically have a "shredded wheat" appearance when viewed with a microscope. If the SiO 2 particles fed to the process had angular moφhology, the resulting particles will have a more regular moφhology (i.e., less angularity). Suφrisingly, it also has been found that pellets pressed from the particles possess unexpected properties when heated. For example, those pellets pressed from silica particles produced by heating to temperatures in the range of about 450°C to about the temperature at the liquidus curve display a very low dimensional change, i. e., average volume change, of about ±0.5% when heated over the temperature range of 100°C to 900°C. The particles produced by heating to this temperature range typically have bulk densities in the range of 0.6 to 0.9 cc/g. Those pellets pressed from silica particles produced by heating to temperatures above the liquidus curve possess the unexpected property of having an Initial Negative Thermal Expansion Coefficient when heated. The term "Initial Negative Thermal Expansion Coefficient" as used herein is defined as meaning that pellets consisting of the SiO 2 particles actually shrink the first time the pellets are heated to a temperature in the range of approximately 100°C to 400°C, using the test method described in Example 1. This phenomenon may be observed over only a portion of the 100°C to 400°C range in order to satisfy the definition. The particles produced by heating to this temperature range typically have bulk densities in the range of 0.2 to 0.6 cc/g, preferably 0.3 to 0.5 cc/g. Without being bound by theory, it appears that internal particle voids contract (irreversibly) within at least a portion of the 100°C to 400°C temperature range, at a rate higher than thermal expansion of the SiO 2 , causing a net reduction in pellet (and particle) size. Figures 2 and 3 reflect this phenomena for pellets prepared from two representative lots of particles in accordance with the invention and are discussed further in the Examples. While the above describes the particle properties being distinct depending on the temperature to which the mixture of boron oxide and silicon dioxide are heated, it should be recognized that depending on temperature, soak time and the composition of the mixture, a continuum of properties can be achieved which encompasses the range of potential variable combinations. INDUSTRIAL APPLICABILITY The particles may be used in conventional applications for silica particles. Moreover, the properties discussed above make the particles particularly suited for specialty applications requiring an inexpensive SiO 2 having low density, a porous structure, or more regular particle moφhology. For example, the relatively large surface area to volume ratios of these particles makes them potential candidates for use as catalyst supports, adsorbents, thickeners, viscosity and/or rheology modifiers and chromatography media. Also, the internal pores can be impregnated with a liquid and the particles employed as a delivery or containment vehicle. The high degree of internal porosity, which can trap air, also makes the particles useful as a filler in specialty polymer insulation formulations. Entrapped air also lowers the dielectric constant of the particles, making them useful as a filler for polymers used in electronic applications. The particles may be also particularly suited for use as a filler in polymers employed in electronic packaging. The Initial Negative Thermal Expansion Coefficient can be used to help offset the typically high thermal expansion coefficients of organic resins used in electronic packaging. Thus, the resin may be designed to have an overall thermal expansion coefficient similar to that of the intended substrate or component to be encapsulated. In this way stresses (e.g., "thermal mismatch") created during the fabrication can be minimized. Also, due to the regular moφhology of the particles, the particles are less likely than conventional mechanical silicas to become lodged between connector wires as the polymer composite is cast into place. The particles may also be useful in numerous applications such as in adhesives, cosmetics and personal care products, greases, rubbers, coatings, sealants, pharmaceuticals, composites, foods, and inks. Having described the invention, it now will be illustrated, but not limited, by the following examples. EXAMPLES Example 1 12 grams of silica powder, SiO 2 (Minsil 40, commercially available from Minco Inc.), was dry mixed with 21.2 grams of boric acid, H 3 BO 3 (GR powder from EM Science Industries Inc.) in an alumina crucible. A small amount of deionized (DI) water was then added and stirred in to make a mix with a paste-like consistency. This procedure was repeated again in a second alumina crucible. The two crucibles were then covered, placed in a small box furnace, and heated to 1000°C and held at that temperature for four hours. The temperature was then lowered to 500°C and held there for thirty minutes followed by turning off the power to the furnace and allowing the two crucibles to cool to room temperature. The crucibles were then immersed in about 3.5 liters of DI water in a 4 liter glass beaker and manually scraped so as to remove the friable-like powder pellet which had formed in each crucible. The powder/water mixture was then heated to about 90°C while being agitated for one hour to solubilize the B 2 O 3 and isolate it from the SiO 2 powder. The mixture was allowed to cool to room temperature and then was reslurried and allowed to set for 30 minutes. A major fraction of the powder, designated as A, was observed to have settled out of suspension while a minor fraction, designated as B, was observed to still be suspended in the water. This B fraction was decanted off to another 4 liter beaker and allowed to settle overnight. The A powder was transferred to a Buchner funnel with filter paper and was washed with 8 liters of DI water. After the B fraction had settled out of solution the water was decanted off and the powder was reslurried with another 4 liters of DI water and isolated by transferring to a filter. Both powders were dried in a vacuum oven at 130°C for 12 hours. The weight of the A powder was 16.7 grams and the B powder was 6.3 grams. The total yield of 23 grams agrees well with the starting weight of 24 grams of SiO 2 powder that was used. Three grams of the Minsil 40 and A and B powders were each charged to a lOcc graduated cylinder and manually tapped 30 times to give approximate tap densities of 1J4, 0.50, and 0.32 g/cc, respectively. X-ray diffraction data, surface areas, particle size distribution parameters dl6/d50/d84/dmax as measured by laser light scattering, and mercury and nitrogen porosimetry data were collected to characterize the three powders. The results are provided in Table 1. Table 1 *(Hg) and (N 2 ) represent data obtained from mercury and nitrogen porosimetry, respectively. In addition to the above data the powders were characterized in terms of their thermal expansion behavior using a thermal mechanical analysis, or TMA. The data were collected using a Thermomechanical Analyzer, model # 2940, made by TA Instruments. The powders were pressed into cylindrical pellets with approximate dimensions of 7mm in diameter and 3mm in height at a force of 2,000 pounds. The pellets were then heated at about 10°C / min up to 950°C and the relative change in the height dimension was measured. These data are plotted in Figures 2, 3, and 4, where the x-axis is temperature and the y-axis is % dimension change. Figure 4 is the TMA data for the Minsil 40 powder. It shows a fairly typical behavior for a powder comprised of dense silica particles, expanding from about 100°C to 600°C and reaching a maximum expansion of about +0.5% at 600°C. The pellet made from the A fraction powder exhibits a marked contrast in its TMA data shown in Figure 2. In this case, the pellet is observed to contract from about 100°C to 400°C, yielding a contraction, or negative thermal expansion, of about -1.1% at 400°C. Upon further heating the pellet undergoes a linear expansion up to 950°C. The pellet made from the B " fraction of powder also exhibits a different trend in its TMA data as shown in Figure 3. In this case, the pellet is observed to exhibit a contraction from about 100°C to about 200°C of about -0.4%. It then remains flat until about 300°C at which time it exhibits an expansion up to about 500°C that peaks at about +0.25% at 500°C. A further increase in temperature results in a contraction of the pellet equal to -4.0% at 950°C. These pellets were cooled to room temperature and then run again using the same temperature profile. The TMA curves for the second passes are illustrated with a dashed line. The character of these curves is quite different from that of the original TMA data. In particular, Figure 2 shows a slight expansion up to about 0.3% upon reheating from 100°C to 500°C. This is very different from the initial heating of that pellet which exhibits a contraction of about -1.1% at 400°C. This implies that the observed negative thermal expansion is a one time phenomenon over the temperature range of about 100°C to 400°C, and is not reversible. Comparative Example 2 The Initial Negative Thermal Expansion Coefficient exhibited by the pellet made from the A fraction powder of Example 1 is unexpected and clearly different from that of a pellet comprised of dense silica particles as shown in Figure 4. Such behavior could be indicative of high surface area powders and/or powders comprised of particles possessing a high degree of internal porosity. To determine if this is true three commercially available powders were measured using TMA and the procedure as defined in Example 1. The silica powders used were: a) Cab-o-sil(R), fumed amoφhous silica, Grade PTG, made by CABOT Coφoration and two different silica powders obtained from Alpha Aesar, a Johnson Mathey Company located in Ward Hill, Mass., defined as b) an 8 mesh material, catalog # 89346, with 1 cc/g of porosity, and c) a 58 micron powder, catalog # 89385, with 1 cc/g of porosity. The TMA data for the pellets made from the Example 2-a, b, and c powders are shown in Figures 5, 6 and 7, respectively. Figure 5 shows a curve similar in character to that of the pellet made from the Minsil 40 powder given in Figure 4. Figures 6 and 7 are similar in character but quite different from the trends exhibited in Figures 2 and 3. In these cases the pellets are observed to show approximately zero thermal expansion from 100°C to about 300°C. After 300°C both pellets exhibit a negative thermal expansion up to 950°C, resulting in total negative thermal expansions of approximately -5 and -6%, respectively, at that temperature. Properties of the particles were measured using the procedures of Example 1 and are provided in Table 2. Table 2 *(Hg) and (N 2 ) represent data obtained from mercury and nitrogen porosimetry, respectively. None of the pellets made from the powders of Example 2 exhibit an initial negative thermal expansion over the temperature range of 100°C to 400°C , as is the case for the pellet made using the A powder fraction from Example 1. Example 3 A blend of 650 g silica powder (Minsil 40, commercially available from Minco Inc.), and 621.6 g of boric acid (Boric Acid Technical Granular from U.S. Borax Inc.) were blended by shaking in a 1-gal plastic bag. The mixture of powders was charged to a 10 in. x 10 in. x 2 in. alumina sagger containing about 550 ml of deionized water. The mixture of powders and water was stirred to give a thin paste. The sagger was placed in a box furnace to about 500°C and the temperature maintained at about 500°C for about 4 hrs. The sagger was allowed to cool slowly in the closed furnace to about 85°C. The sagger was immersed in 7 to 8 liters of hot tap water. This procedure aids in the removal of boron from the product silica as water soluble boric acid. The resulting slurry of silica in aqueous boric acid was heated at about 75°C for about 1.5 hrs. The slurry was filtered and the cake washed with deionized water until the filtrate density was about equal to that of the deionized water. The wet cake was dried in an oven at about 120°C for about 16 hrs to give about 540 g a white silica powder. The properties of the product powder are shown in Table 3 and compared to the Minsil 40. The powder was also characterized in terms of its thermal expansion behavior in a similar process to that described in Example 1. A sample of the powder was pressed into a cylindrical pellet and then heated to a temperature of 950°C and the relative change in the height dimension (volume) was measured. The data are plotted in Figure 8. The pellet is observed to change in dimension (volume) of a maximum of less than 0.07%. Example 4 The process of Example 3 was repeated to with a silica/boric acid mixture having a ratio of 25% B 2 O 3 and 75% SiO 2 . The properties of the product powder are shown in Table 3. Table 3 As can be seen from Table 3, the products of Examples 3 and 4 show increases in surface area and pore volume, and decreases in bulk density indicating a more porous product.

Claims: WHAT IS CLAIMED IS: 1. A process for preparing silicon dioxide particles comprising, in sequence: a. forming an intimate mixture of silicon dioxide particles and at least one boron compound selected from the group consisting of B 2 O 3 and boric acid; b. heating said intimate mixture to a temperature above about 450°C for a time sufficient to alter the density and/or moφhology of said individual silicon dioxide particles; c. cooling the mixture to ambient conditions; and d. recovering discrete silicon dioxide particles. 2. The process of claim 1 including the step of removing water from said intimate mixture prior to heating the mixture to the melting temperature of B 2 O 3 . 3. The process of claim 1 wherein the mixture heated in step b consists essentially of 20 to 70% B 2 O 3 and 80 to 30% silicon dioxide particles, by weight. 4. The process of claim 3 wherein the silicon dioxide particles contained in said intimate mixture of step a are crystalline. 5. The process of claim 4 wherein the silicon dioxide particles contained in said intimate mixture of step a are amoφhous. 6. The process of claim 1 or 3 wherein the mixture is maintained at the temperature of step b for 1 to 20 hours. 7. The process of claim 1, wherein in step b, said intimate mixture is heated to a temperature of from about 450°C to the temperature at the liquidus curve of said mixture. 8. The process of claim 1, wherein in step b, said intimate mixture is heated to a temperature above the liquidus curve of said mixture. 9. The process of claim 7, wherein prior to step c, at least a portion of the liquid B 2 O 3 is removed from the particulate SiO 2 while maintaining a temperature above 450°C. 10. The process of claim 8 wherein, in step c, the liquids sequentially are: (i) cooled to a temperature between the melting temperature of SiO 2 and B 2 O 3 for that mixture; (ii) at least a portion of the liquid B 2 O 3 is removed from the particulate SiO 2 while maintaining the temperature of (i); and (iii) particulate SiO 2 and any remaining B 2 O 3 are cooled to ambient temperature. 1 1. The process of claim 9 or 10 wherein liquid B 2 O 3 is removed in by filtration. 12. The process of claim 9 or 10 wherein at least a portion of residual B 2 O 3 contained in or on the recovered SiO 2 particles is removed by washing said particles with water. 13. Silicon dioxide particles that have an average volume change of about ±0.5% over the temperature range of 100°C to 900°C. 14. Silicon dioxide particles that have an Initial Negative Thermal Expansion Coefficient over at least a portion of the temperature range of approximately 100° to 400°C. 15. The particles of claim 13 having a bulk density in the range of 0.6 to 0.9 g/cc. 16. The particles of claim 14 having a bulk density in the range of 0.2 to 0.6 g/cc. 17. The particles of claim 14 having a bulk density in the range of 0.3 to 0.5 g/cc.

Inventors: BRUNO SALVATORE ANTHONY, SWANSON DONALD KEITH, BRUNO, SALVATORE, ANTHONY, SWANSON, DONALD, KEITH
Applicants: DU PONT, E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1998
Main classification: C01B33
IPC codes: B01J20, B01J21, C01B33, C08K3