JP2019520989A - In-situ formation of aqueous, semi-aqueous, non-aqueous slurry suspensions of viscous particles for the purpose of separating and suspending inert particles and abrasive particles in dispersion medium - Google Patents

Abstract

A stable aqueous, semi-aqueous or non-aqueous suspending medium for suspending inert organic or inorganic particles in the suspending medium. Gel particles are contained as a separating agent for inert organic or inorganic particles, and the inert particles are prevented from settling and aggregating hard by the gel particles over a long period of time.

Description

  The present invention relates to sol or gel particles which are present as suspension medium in a single or liquid medium. More particularly, the present invention provides a carrier system having long-term dispersion stability characteristics of particle suspensions, referred to herein as soft settling characteristics. The carrier system uses a wide range of suspendable inert particles, including abrasive, non-abrasive, inert organic particles and ceramic particles, for lapping, wire sawing, chemical mechanical polishing and / or metal formation and It is used for flattening in finishing, free abrasive grinding and the like.

  Non-aqueous, semi-aqueous and aqueous suspensions of non-colloidal high density abrasive particles have been used for wire sawing and lapping of wafers until now, but the separation of inactive particles in the suspension is prolonged It was not possible to obtain a stable particle suspension which could be maintained. U.S. Pat. No. 5,099,820, obtained by Stricot, discloses an abrasive slurry of a suspension of silicon carbide particles in water or oil. However, this suspension is not stable and can not provide uniform lubrication and cutting by the wire. This composition requires vigorous stirring to maintain uniform suspension of the particles, and the suspension rapidly settles even during slicing of the object under stagnant conditions even while stirring.

  US Pat. No. 6,602,834 to Ward et al., Which is incorporated herein by reference as part of this specification, is surface active to provide electrostatic repulsion and particle interference to maintain a stable suspension of abrasive particles. Disclosed are cutting and lubricating compositions for non-aqueous or semi-aqueous wire saws that depend on the agent, the organic polyelectrolyte and the pH. U.S. Pat. No. 6,054,422 to Ward et al., Which is also incorporated as part of the present specification, uses a mixture of high and low molecular weight polyalkylene glycols as a suspending agent, up to 70 wt. Disclosed is a lubricating composition containing at least 1% abrasive grit material.

Wafers in the manufacture of silicon, SiC, sapphire, GaAs, optical glass and other wafers used in microelectronics, solar cells, LEDs, broadband devices, optical / laser, wafer polishing, CMP applications and other diverse industries Are cut from larger ingots, bricks, boule, etc. The steps following first cutting the wafer, disc, chips etc. include lapping the cut wafer to smooth the surface. This reduces TTV (full thickness variation) (does not apply to solar wafers), eliminates flaws on surface defects, and allows final polishing of the wafer condition, ie suitable for semiconductor and optical wafer manufacturing It has the purpose of getting it in a basic state. Generally, an aqueous carrier is used as the suspending medium for the lapping abrasive in this step. Lapping abrasives include, but are not limited to: SiC, aluminum oxide, ZrO ₂ , silica, CeO ₂ , diamond and the like. The lapping slurry utilizes abrasive particles in the size range of about 0.1-10 μm. This means that the wafer-borne suspension abrasive particles are non-colloidal in size and nature. While this does not exclude the possibility of using colloidal particles in the lapping abrasive, ie abrasive particles in the size range of about 0.001-0.5 μm, such particles are not usually used in lapping slurries .

  Lapping slurries used for wafers, mechanical gear sets for the automotive industry, ceramics, etc. are subject to a lot of shear, grinding and polishing forces during the wafer lapping process. In a process called "planetary lapping", the wafer is held between plates made of two large metal (typically iron or steel or both are used) and a slurry is injected on the surface. The upper and lower plates holding the wafer rotate in opposite directions to compress the slurry between the upper plate and the wafer surface. The solids in the compacted slurry contact the wafer and the angular momentum causes the polishing action to remove wafer surface defects and "etch away" any amount of wafer surface material. For all aqueous slurries used today for lapping, such effects on the slurry and the mechanism of the lapping apparatus propagate particle aggregation on the wafer, in the reservoir, in the supply piping, in the wrapper, on the metal plate, and the like. Such particle agglomeration has the deleterious side effect of causing so-called "dark scratches" which damage the lapped wafer. Wafers with dark scratches need to be disposed of at great cost.

  The problem of non-colloidal, ie, NCOL, aqueous suspensions of high density abrasive particles has been plaguing and wasting wafer manufacturers over the past few decades. To date, there has been no low viscosity aqueous carrier capable of maintaining the NCOL abrasive particle suspension beyond a very short period of a few minutes or so. After that time, the abrasive particles start to flocculate and separate from the suspension as a very hard "concrete-like" solid and settle rapidly to the bottom of the vessel. Such settling of the abrasive particles in currently used "aqueous" slurries occurs rapidly, as well under conditions of continuous mixing or recycling.

  Once the particles settle out and become a hard, deposited solid at the bottom of the container, it is very resistant to attempts at resuspension by any means. With simple mixing, stirring, shaking, and the like simple methods, regeneration of the slurry to maintain the original particle size distribution of the abrasive prior to settling can not be achieved. As a result, such slurries become unusable and must be discarded immediately, wasting expensive abrasives, time, human resources and effort.

  In prior art suspensions, the length of time that the suspension is kept uniform and uniform over long periods of stagnant storage is determined by temperature and pH. Inorganic particles can remain in suspension in aqueous and non-aqueous solvents, depending on particle size, lattice structure and density, but in stagnant storage conditions tend to aggregate and precipitate out of suspension. Also, there are no suspending agents that can be made depending on the application. The suspending agent remains in the same medium as formed.

  The overall objective of the present invention is to provide a wide variety of gel particles from a wide variety of compounds, polymers, and materials under a wide range of conditions. There, gel particles are formed in-situ from various combinations of various forming conditions and compositions of raw materials, and various kinds of various in-situ forming media including organic, inorganic and semi-organic, and all of them are stable. It has the property of providing long-term inert particle separation and suspension in the slurry suspension. These stable slurry suspensions are used in wire saw applications, lapping applications, CMP applications to cut ingots or other large materials into wafers, disks, or other machined, sliced, ground or shaped pieces It can be used for machining, grinding and milling applications, metal gear forming applications for automobiles, optical and optoelectronic sheet processing, grinding and lapping applications, and particle separation.

  It is also an object of the present invention to provide gel particles formed in-situ in non-aqueous media, and these examples also have the same performance and suspension characteristics as gel particles generated in-situ in aqueous media As well as providing gel particle properties. These non-aqueous gel particles consist of polyacrylic acid, polymaleic acid, polyalkylacrylic acid or copolymers thereof and are in-situ neutralized in an organic medium, preferably polyethylene glycol, polypropylene glycol, diethylene glycol or other glycols Alternatively, partial neutralization is preferred for producing typical gel particle species in the forming medium that meet the same suspension characteristics as other gel particles. The gel particles formed in the non-aqueous medium also have the typical characteristics of in-situ generated gel particles, which are formed in-situ within the suspension medium used or the gel The particles produced in the particle formation medium are transferred to the next appropriate medium to be utilized as an inert or abrasive particle suspension. However, in the latter case, it is a condition that the second medium does not cause reaction, interaction, influence and performance degradation to the suspension performance of the gel particles in the selected final medium.

  Another object of the present invention is low toxicity, without aggregation or coagulation of the particles in the suspension, which is not practically a problem, and without collecting as a solidified solid at the bottom of the suspended slurry container And / or inactive abrasives or non-active abrasives in a stable long-term stable suspension, provided that they are contained in the carrier with a low to medium viscosity and somewhat less than that of the suspended gel particles of which the density of the suspension carrier is less It is an object of the present invention to provide gel particles having properties that allow for the sustained separation of abrasive particles. Yet another object of the present invention is to provide inert gel particles which exist as colloidal or NCOL abrasives or non-abrasive particles in neutral or near neutral pH media and form a stable suspension. It is.

  A further object of the invention is to provide a means for suspending colloidal or NCOL abrasives or other particles in a liquid independent of the final slurry viscosity. The present invention further aims to provide gel particles which can be added to various base carriers for separating and suspending inert particles and which can also act as a lubricant. A still further object of the present invention is to provide an aqueous or semi-aqueous carrier / slurry system which does not cause corrosion of metals such as iron, carbon steel and the like.

  Other objects will be described in the following contents.

  The present invention relates to sol-gels or gel particles which can be used alone or in an organic or aqueous medium to suspend particles in a carrier and to suspend solid inert particles. Gel particles (hereinafter "gel particles"), including sol-gels, gel particles, gelatinous aggregates etc., suspend the inert particles and act as a lubricant in the particles alone or in a liquid medium in various applications used. The suspension slurry composition formed can contain gel particles in an amount ranging from about 0.1% to about 60% by weight of the carrier. Gel particles and base carriers can be used without the addition of other suspended particles as a lubricant. The carrier can contain about 1 to 100% by weight water, and less than 100 percent water can add an organic solvent to any carrier. The organic medium can include various solvents, but it is inert and non-reactive in aqueous medium and can be used as a solvent capable of suspending gel particles (including abrasives suspended by gel particles) depending on the application And polyalkylene glycols are preferred. Suspended gel particles have a density comparable to or somewhat greater than the carrier-solvent composition.

Gel particles for suspension by in-situ aqueous formation are aluminum hydroxide (Al (OH) ₃ ), magnesium hydroxide Mg (OH) ₂ , zinc hydroxide Zn (OH) ₂ , copper hydroxide Cu (OH) ₂ and the like are preferred and can be produced in an aqueous or aqueous based medium, separated and transferred to an aqueous or non aqueous second medium or used alone in various cases. Gel particles may be required to specialize in the production of suspensions or slurries of stable suspension abrasives or non-abrasive particles generally referred to as lubricants or slurries. However, gel particles can also be formed with other metal sulfides, hydroxides and oxide hydrates as long as they can form a suspended precipitate in water within the pH range of 3-12.

  The invention includes methods of suspending an inert colloidal or non-colloidal abrasive or non-abrasive inert particle in a stable aqueous, semi-aqueous or organic carrier medium. The carrier medium is a liquid in which the suspended particles are formed in-situ, establishing a suitable concentration of suspended particles relative to the inert particles, sufficient for settling of said inert particles in said carrier medium Causes interference. The carrier medium comprises suspended particles in the range of 0.1 to 60% by weight. The suspended particles are different from the above-mentioned inactive particles and are selected from the group consisting of alkaline earth metal and transition metal hydroxides, oxyhydroxides, and oxide hydrates, as described above in the range of pH 4 to 12 The above-mentioned suspended particles are formed in-situ while being contained in a carrier medium of The in-situ formation of suspended particles in the carrier medium is distinctly different from the carrier medium in molecular, configurational, rheological and physical structure, the density higher than the density of the carrier medium, the carrier medium and the visual Include distinct physical structures that can be identified, measurable size differences in the range of about 2-3 μm to 500 μm, and molecules of the carrier medium in which suspended particles are formed, but without further chemical reaction (but The interaction between the gel particle structure and the carrier molecules contained therein is possible and occurs with considerable potential), resulting in suspended particles exhibiting a series of fairly homogeneous properties. Finally, suspended particles exhibit these properties regardless of their formation mechanism or the origin of the components.

As a direct result of the in-situ formation of the suspended particles, the inactive particles are not physically interfered with the suspended particles and the inactive particles, among the attractive forces of force between the suspended particles and the inactive particles. Suspended in the carrier medium by at least one of This results in proximity that leads to chemical, physical or physicochemical interference and electrostatic repulsion of the suspended particles against the inert particles and themselves, all of which result in the long term of said carrier medium over a long period of time. Prevent aggregation and coagulation of inert particles.
The components that make up the in-situ formed suspended particles may be gel particles, sol-gel particles, or gelatinous precipitates of many compounds, which are described in more detail below. In addition, depending on the composition of the suspended particle components, the suspended particles can be formed in a medium separate from the final carrier medium.

The present invention provides a means for forming or generating a wide variety of gel particles under a wide variety of conditions from a wide variety of compounds, polymers, and materials.
The in-situ formation of gel particles here is carried out with a wide variety of different forming conditions, constituent material compositions, and a combination of various in-situ forming media spanning organic, inorganic and semi-organic matrices, sol-gel or gel particles To provide a stable suspension without coagulation or hard settling of inert or abrasive particles in aqueous, semi-aqueous, or organic media. This suspension is used for cutting, slicing, grinding, etc. slurries stabilized by the "stable properties" which is an advantage of gel particles, and is used for cutting, slicing, machining, grinding, milling, lapping, re-cutting. It is used for the purpose of processing molded, hard materials into finished pieces including, but not limited to, wafers, disks, special hard metals, semi-metals, or ceramic parts.

  One of the features of the present invention is the suspension of the slurry used for cutting or slicing, lubricants, lapping or polishing slurries, non-abrasive slurries, and particles of similar wire saw applications unchanged by ambient temperature and elevated temperature Liquid and / or lubricious carrier and slurry compositions are provided. The gel particles are maintained as about 0.1 to 80% by weight aqueous, semi-aqueous or non-aqueous suspension in the carrier medium, whereby sufficient interparticle interference is present against aggregation or hard settling of the abrasive or inert particles. I will provide a. The gel particle density is somewhat greater than the density of the carrier medium. The gel particles may be prepared alone and used alone or in a carrier as a lubricant and / or suspending agent, or in combination with a suitable polar or nonpolar solvent depending on the suspension compatibility of the gel particles with the carrier medium be able to. As an example, gel particles can be used in different types of glycols, which have the advantage of obtaining specially made lubricating compositions specific to particular applications.

  In many cases, it is desirable to use two or more suspending agents in order to obtain uniform dispersion over as long as possible. The reason is that the particles to be suspended may have different density and / or static charge than the suspended gel particles. For example, in a wire sawing operation, there are particles for cutting and particles originating from the cutting of the ingot being cut. In other operations, impurities with higher or similar density than the suspending medium may be present.

  Taking the aqueous case as an example, these suspended particles are hydroxides, oxyhydroxides, and oxide hydrates (hydrated oxides) of in-situ formed alkaline earth metal or transition metal. Also form suspended particulate precipitates, ie, sol-gels, gel particles, gelatinous precipitates, etc., in an aqueous or semi-aqueous medium at a pH in the range of about 3-12. The particles to be suspended are conventional abrasive or non-abrasive particles, inert particles, for pigment production, wire saw cutting, metal finishing applications and wafer lapping applications with a particle size of about 1 to 100 μm, for wafer lapping applications Generally, smaller particle sizes of about 0.1 to 10 μm and even smaller ones of about 10 to 500 nm are used for CMP applications. The suspended particles are preferably formed in-situ, or separately as in the case of forming metal hydroxides from metal salts. In such cases, the density of the in-situ prepared precipitated gelatinous gel particles is greater, and the in-situ formed gel particles can be obtained in the "dry" form available when the same gel particles are commercially available. The surface area is smaller than that. The in-situ formed gel particles generally retain a higher density than the in-situ carrier medium, or any second medium in which the formed "gel particles" are disposed. In addition, in general, gel particles formed in situ according to the present invention exhibit a broader particle size distribution. An advantage of separating the gel particles from the carrier medium is that it allows the mixing of particles of different particle sizes for specific applications, in particular for use in coatings.

  Abrasive materials of the above composition include diamond, silica, tungsten carbide, silicon carbide, boron carbide, silicon nitride, silicon dioxide, cerium oxide, zirconium oxide, powder of aluminum oxide, or other hard particles. "Material can be used. Generally, the average or standard particle size is about 0.5 to 100 microns, preferably about 2 to 50 microns, or a mixture within these ranges. The concentration of inert particles suspended in the suspending medium or carrier for most applications typically falls in the range of about 0.1 to 60% by weight of the total suspension.

  Solvents that can be used with the aqueous medium are polar solvents including alcohols, amides, esters, ethers, ketones, glycols, glycol ethers, alkyl lactones, or sulfoxides. Specific examples of polar solvents include dimethylsulfoxide (DMSO), dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), (gamma) γ-butyrolactone, diethylene glycol ethyl ether, dipropylene glycol methyl ether, tripropylene glycol Monomethyl ether, various glycols, polyethylene glycol, polypropylene glycol and the like can be mentioned.

  Organic solvents may be used to provide the required viscosity level to the slurry obtained in preparation. Other uses of organic solvents include lowering the freezing point of the slurry / carrier. The choice of solvent is such that the solvent is inert or completely miscible or soluble in water and, in the case of aqueous forming gel particles, non-reactive with the water or the suspended or suspended gel particles. It is relatively unimportant as long as it is low toxic and low odor.

  As suspended particles usable in the case of aqueous forming gel particles, metal hydroxides, oxide hydrates (or hydrated oxides) and oxidations other than abrasive particles forming aqueous or semi-aqueous suspensions Substances such as, but not limited to, gel particles, gelatinous precipitates, sol-gels, colloidal or non-colloidal suspensions and the like. These suspended particles, which are an important component of the present invention, may settle towards the bottom of the container with the passage of time, but with the passage of time a "cake" of hard agglomerates or particles at the bottom of the container It does not form. This uses potassium hydroxide, tetramethylammonium hydroxide, sodium hydroxide, sodium carbonate, tetraethylammonium hydroxide, tetraethylammonium hydroxide, etc., metal or nonmetal Bronsted bases such as shown in the examples of the following formula: Included are, but are not limited to, compounds present in-situ in or without medium converted to hydroxide form (such as metal sulfates).

  An insoluble completely suspended gelatinous precipitate or a precipitate of aluminum is formed at a pH in the range of about 4-12.

Metal hydroxides suitable for use in the examples of aqueous forming gel particles according to the invention include copper hydroxide, aluminum hydroxide, barium hydroxide, ferrous hydroxide or ferric hydroxide and Zn (OH (OH) ₂ ), but not limited thereto. The metal sulfides, salts or oxidized hydrates that can be used to form suspended particles in the aqueous example of the present invention or to form in-situ include Zn-salts, ZnS, SnO ₂ x H ₂ O, tin salts, There are transition metal oxides such as SnS, Al ₂ O ₃ x H ₂ O, and Al-salts. These salts, sulfides, oxyhydroxides, oxide hydrates (or hydrated oxides) and the like are used to form the corresponding hydroxides, and sol-gels for the example aqueous carrier systems of the invention It is also possible to obtain stable suspension media comprising gel particles, and gelatinous particle suspensions. In the case of Al (OH) ₃ or other aluminum oxide, or hydroxide species, the pH range for use in the carrier is about 3-12. The preferred pH range is 5 to 10, and the most preferred pH range is 6 to 9.

  Included as suspended precipitates or gel particles are particles having a density greater than the density of the carrier solvent, and particles that exhibit precipitation or suspension in nature. Metal oxyhydroxides, hydroxides or hydrated oxides of higher density except when formed or precipitated in situ in aqueous or semi-aqueous media and then added to the carrier system of the present invention It is known to exist.

  A precision measurement device was used to quantitatively measure the level of the "soft settling" property of the abrasive slurry (SiC slurry). The slurry stability of a particular suspension carrier is assessed by its soft settling and holding characteristics (SSR), in other words the size of the solid suspension's resistance to forming a hard cake at the bottom of the container. It is also evaluated by the suspension volume retention (SVR), which measures the efficiency with which solid particles remain separated from one another in suspension. In order to determine whether the carrier can produce a stable slurry, prepare a slurry containing 15-25% silicon carbide (SiC) JIS 1000 grade (average particle size about 13-16 μm), 50 ml graduated The tube was placed in a test tube having a conical bottom, and both SSR and SVR were measured over a long period of time under a room temperature and 50 ° C. environment.

  An IMADA vertical manual lever force test bench, model LV-100, was used to measure the soft settling characteristics. The IMADA pushes a probe with a circular pad of reference diameter at the bottom of the shaft against the slurry and measures the force required to pass through the slurry to reach the bottom of the vessel. In order to measure the force required, the shaft of the probe is elongated so that the probe can be extended and reached to a point within 1 mm from the conical bottom of the graduated test tube, the diameter of the bottom and the diameter of the probe The IMADA configuration was modified to make the difference less than 1 mm. The probe was lengthened by attaching an elongated threaded rod to the probe. Forces measured by IMADA are reported in hundred pounds. A low SSR indicates that the abrasive can be easily re-suspended, and high values above 1.0 indicate that the abrasive is hard to settle and can not be easily re-suspended.

  Suspension volume retention [SVR] measures the volume (ml) of the solid occupied in the test tube and divides that volume by the total volume (ml) of the slurry in the graduated test tube, as a result Calculated by multiplying the percentage reading by 100. Generally, but not always, the higher the SVR value, ie, closer to 100%, the better the ability of the carrier to hold the abrasive in suspension. Although the SVR of a slurry generally decreases with time, it does not necessarily indicate the soft settling characteristics of the slurry. Randomly, the measured value of SVR does not match the expected value under the conditions of the "soft settling" experiment of the slurry under investigation. In other words, SVR is a qualitative indicator, but in contrast to the much more accurate and consistent quantitative soft settling property [SSR] values, the consistent value expected for "soft settling" slurries is I can not get it. Hence, SVR, although not always but often suggestive, can not be a quantitative measure of the overall stability of a slurry like SSR.

  The degree of stabilization of the abrasive slurry suspended by the typically formed gel particles described as part of the present invention, and the irregularity between the SSR value over time of the stored slurry and the SVR of the same slurry The following cases are typical examples of such intuitive relationships.

  An apparently non-aqueous gel particle suspension carrier was formed in situ with PEG-200 in the following manner. Suspended gel particles were formed by partial neutralization of a copolymer of acrylic acid and maleic acid with a final molecular weight of> 3000D. The aforementioned polymer was initially purchased as a 50/50 (wt / wt) aqueous solution and added to the suspension carrier PEG-200 to obtain a clear to slightly cloudy solution of the copolymer acid. This polymeric acid uses amino hydroxide base until appropriate gel particles are formed in the PEG suspension medium at a concentration sufficient to suspend about 48% of the SiC abrasive on a wt / wt basis And was partially neutralized.

  After cutting a large number of Sii ingots into wafers using this slurry, the slurry is "consumed" and stored in a 4x4x4 inch 300 gallon container with a total weight exceeding 3000 pounds per 3 containers It was done. The spent slurry was "cold stored" in stagnation for 4 years in an environment where temperature and / or humidity are not controlled. The "soft settling" property of the long-lived spent slurry was qualitatively measured using a 5 inch long steel shaft (extended size IMADA rod) with a circular disc of 8 inches or less in diameter at the end of the shaft. The "IMADA rod" was gently dropped into the slurry in each container without external force, and the hardness of the precipitated solid was qualitatively measured. The SVR measurement of these solids was <30%. The IMADA rod was able to fall to the bottom of the slurry in the container without external force and exhibited a SSR of ~ 0 even after 4 years of stagnant storage.

  This experiment was repeated with at least 12 other glycol-based non-aqueous spent slurry storage containers, but similar results were obtained in all cases. Such "soft settling" in high solids content slurries after 4 years clearly demonstrates the effectiveness and persistence of the inventive separation and suspension property concept of the gel particles.

  Both the penetration depth of the standard rod and the calibration of the tool so that the measuring tool used to measure the soft sedimentation resistance (SSR) accurately measures the "cake penetration resistance" in a repeatable and accurate way I checked every day. For slurries formed in superior suspension carriers, the penetration SSR was low and was expected to be as low as <0.1 pounds for long term storage up to 4 to 6 weeks under controlled test conditions. For example, for slurries formed in gel particles such as standard PEG-200, -300, or -400, or in the presence of inferior suspension carriers in the absence of water, measurement of soft sedimentation resistance with storage times as short as several days The value typically showed a high range of 1.5-2.0 pounds. In other words, the lower the SSR for a given slurry over time, the better the performance, stable storability, prevention of solidification or aggregation of the individual over time, maintenance of the slurry suspension, recyclability, and long term storage It is a more stable, uniform, ie better quality slurry, with regard to the ease of retention of the original slurry suspension properties later.

  Since the present invention relates to aqueous, non-aqueous and semi-aqueous media, carbon steel, iron, spring steel etc. where the composition of the present invention is a typical component such as wire saw, metal finish wrapper, wafer wrapper etc. Prolonged contact with metals can cause metal corrosion and rust. If desired, corrosion inhibitors can be added to the carrier formulations of the present invention to inhibit or eliminate metal corrosion. As a suitable inhibitor, it causes foaming, interferes with the ability to provide a stable abrasive or solid suspension over time, or the viscosity, rheology of the carrier formulation and the abrasive or solid suspension associated therewith It is necessary to use one that does not lose uniformity or uniformity.

  Suitable corrosion inhibitors which can be added to the aqueous and semi-aqueous carriers of the invention include aliphatic and aromatic carboxylic acids, neutralized carboxylic acids using alkanolamines (diethanolamine, monoethanolamine etc), tetraalkyls Ammonium hydroxides, other similar non-metal hydroxide bases, alkyl or aromatic amines, or other Br ス テ ッ ド nsted bases, etc. include but are not limited to these. In addition, metal corrosion inhibitors such as long chain modified carboxylates commercially available under the tradenames DeForest DeCore-APCI-95, DeTrope CA-100, etc. as known in the art may also be included. Further known corrosion inhibitors equally suitable for corrosion protection or inhibition of metals used in CMP processes (ie Al / Cu, Cu, Al / Si, Al / Si / Cu, GaAs, LnP etc) Examples include benzoic acid, pyrogallol, gallic acid, ammonium thiosulfate, 8-hydroxyquinoline, catechol, benzotrizole, triethanolamine, imidazole (such as benzimidazole and alkyl substituted benzimidazole), thiophene compounds such as sulfolane, modified polyacrylics Examples include, but are not limited to, acids or polyacrylates, polysaccharides, polyalcohols such as polyvinyl alcohol, or combinations thereof. Additionally, there are other suitable corrosion inhibitors which function as oxygen absorbers or scavengers. This includes but is not limited to p-hydroquinones (such as p-quinol), polyhydroxyaromatics such as catechol or gallic acid, 8-hydroxyquinoline, nitrites, sulfites.

The choice of corrosion inhibitor for the application of the present invention is not critical as long as the inhibitor meets the aforementioned performance criteria (including those listed below).
-Suppress or eliminate metal corrosion.
Does not cause significant foaming of the carrier or resulting slurry.
Does not impair or interfere with the ability of the suspension carrier to provide long-term stability of the suspension.
No adverse effect on the viscosity, performance or rheology of the carrier or of the resulting gel particles or of the inert solid suspension.
Does not adversely affect the homogeneity or homogeneity of the carrier suspension or gel particles or inert solid suspension in the carrier.
It does not react chemically with the gel particles or inert particles of the base medium or carrier when the slurry is suspended by the gel particles.

  Certain salts produced as by-products of the reaction to form gel particles appropriately increase the ionic strength by providing appropriate concentrations and structures, help with repulsion, and of suspension inactive particles. Increase the time it takes to settle. However, depending on the application of the entire slurry suspension, the resulting dissolved salt formed during gel particle formation is rinsed off and only the in-situ formed gel particles are neutralized or partially neutralized base medium (this It may also be advantageous to leave in case water is preferred.

  The following examples illustrate the practice of the method of the present invention. However, the listed embodiments should not be construed as limiting the full scope of the present invention, and in light of the above guiding principle, it should be understood that the present specification is intended to cover various modifications. It is. All percentages stated herein are by weight unless otherwise noted.

Example 1
A. Preparation of Gel Particles : Solid aluminum sulfate hexadecahydrate was added to tap water so that the percent aluminum sulfate in the water was 10.76%. The solution was neutralized to pH 7.7 with constant mixing for 30 minutes with a 25% solution of tetramethyl ammonium hydroxide (TMAH). The appearance of the obtained Al (OH) ₃ gel particles is a white suspension. The suspension is then rinsed three times with water to remove salts of byproduct products dissolved in the suspension. The ionic nature / properties of the resulting carrier suspension are very low or not at all.

B. Preparation of Suspension Slurry of Abrasive Particles-The gel particles of part A are filtered and a concentrate of the gel particles is added to an aqueous carrier to a specific gel particle concentration. To this aqueous suspension is added dry titanium oxide solids to a total solids content of 25% and a gel particle content of about 10% or less as a composition for coating applications. The data of Soft Sedimentation Resistance (SSR) and Suspension Volume Retention (SVR) of this formulation are shown in Tables 1a and 1b below.

  For solid TiO 2 suspension slurries, an SSR measurement of zero clearly indicates excellent suspension performance. A measurement of a room temperature SVR of 42% after 4 weeks and an SSR of zero at all measuring points is a result showing that the suspension has excellent "soft settling" properties.

Example 2
A. Preparation of Gel Particles- Solid aluminum sulfate octahydrate was added to tap water so that the concentration of active aluminum sulfate in water was 15.5%. The solution was neutralized slowly and uniformly to pH 7.7 with constant mixing with KOH (25% aqueous solution). The appearance of the in-situ formed gel particles is a white cloudy suspension in a water base.

B. Preparation of Suspension Slurry of Abrasive Particles-A slurry containing ~ 48% SiC particles with an average particle size of 9 to 10 μm or less as an abrasive is suspended in the gel particle carrier prepared in the above (A). The suspension is mixed well and left under both room temperature and elevated temperature conditions to determine the characteristics of soft settling and suspension uniformity. The formulation, viscosity, soft settling retention (SSR) and suspension volume retention (SVR) data are shown in the following table. Again, SSR and SVR measurements show excellent and stable particle suspension even after four weeks. However, it should be noted that SVR is typically expected to be lower at higher temperatures than if the same slurry was at room temperature. In this case, as mentioned earlier, the SVR may indicate that the slurry is a stable "soft settling" slurry while not producing the expected quantitative or qualitative measurements. In other words, "SVR can be a qualitative indicator, but it does not always give the consistent value expected for a" soft settling "slurry ...".

Example 3
Solid aluminum sulfate octahydrate was added to the tap water so that the concentration of aluminum sulfate in the water was 15.54%. The solution is neutralized to pH 7.7 with KOH (25% aqueous solution). To this cloudy carrier system, SiC particles with an average size of about 8-9.5 μm are added. The entire suspended slurry is thoroughly mixed for ̃5 minutes. Formulation, viscosity, SSR, and SVR data are shown in the following table.

  Zinc sulfate or stannous sulfate can be used instead of aluminum sulfate. The formed gel can be used after mixing in a liquid medium after filtration. With regard to slurry stability, the same results as in the previous example were observed. However, in this example, the SVR after 4 weeks at 50 ° C. is 71, which indicates that the slurry is a very stable slurry.

  Inert salts can be added to give the particles additional electrostatic repulsion. Also, the dissolved salt produced by gel particle formation can be washed away with water or a suitable carrier medium solvent to form a gel particle suspension that is relatively less ionic or not at all.

Example 4b
A. Preparation of gel particles-
In this example, instead of using tap water as the solvent, a semi-aqueous solvent using diethylene glycol (DEG) was used. Since aluminum sulfate does not dissolve in DEG, it is necessary to first prepare an aqueous solution of aluminum sulfate and add it to DEG. It is common practice to prepare Al (OH) ₃ gel particles in water and add the formed gel particles to other solvents such as DEG. In this case, a 0.4 M aluminum sulfate solution was prepared and neutralized to a pH of about 7.8 to 8.8 or less with a 25% aqueous TMAH solution. The gel particles were separated from the in-situ formed aqueous medium and then added to the DEG to obtain a gel particle suspension suitable for suspending the lapping abrasive. The SSR, SVR, and viscosity were measured. A soft sedimentation tube was prepared using 18% zirconium oxide (ZrO ₂ ) instead of SiC. The measurement results are shown in Tables 4a-1 and 4a-2 below.

  The SSR results in Table 4a-2 indicate that a stable suspension is present after one week at room temperature if the initial amount is greater than 2.0%. In this case SVR = 0.16, which indicates a very "soft settling" suspension. At 50 ° C., a stable suspension is obtained after one week with an AIS level of 0.49%.

Example 4b
A. Preparation of gel particles-
In this example, as in Example 4a described immediately above, instead of using tap water as the solvent, a semi-aqueous solvent using diethylene glycol (DEG) was used. Since stannous sulfate is not sufficiently soluble in PGME, an aqueous solution of stannous sulfate is prepared, in which Sn (OH) ₂ gel particles are prepared and added to the PGME. In this case, a 0.5 M stannous sulfate solution was prepared and neutralized to about pH 7.9 with a sufficient amount of 25% aqueous TMAH solution. The gel particles were filtered and the wet gel solids were stored under sealed conditions for 4 weeks to maintain the water content within the wet gel solids.

B. Preparation of Suspension Slurry of Coating Particles- This wet gel particle was added to a 2: 1 mixture of water and PGME to make it 33% of the total mixture. To the mixture, titanium dioxide was added in the same amount by weight as the gel particles to form a coating composition. It is also possible to add an appropriate amount of tetramethylammonium sulfate here to provide additional electrostatic repulsion between suspended particles.

Example 4c.
The following formulation is intended to lower the viscosity of the formulation described in Example 4a by diluting the carrier with tap water. The carrier was diluted to 25% and 50% with water, and the concentration of aluminum sulfate was kept constant at any dilution rate. In this example, the case of 50% dilution is shown in the following table. Soft sedimented test tubes were prepared using 18% zirconium oxide (ZrO ₂ ) instead of SiC. The measurement results are shown in Tables 4c-1 and 4c-2.

The SSR results shown in Table 4c-2 show that room temperature slurry when the aluminum sulfate content used to form "Al (OH) ₃ " gel particles in-situ in an aqueous medium is greater than about 0.75%. The minimum acceptable value is shown as the soft sedimentation characteristic of. At 50 ° C., when the aluminum sulfate content exceeds 0.50%, the SSR after one week shows the value of a stable soft settling slurry.

  In this example, it is necessary that the content of suspension gel particles is sufficient to physically and / or physicochemically prevent the level stability of the abrasive particles or inert particles contained in the target slurry. Demonstrate. If the gel particle content is less than that required to adequately prevent abrasive particle clumping, coagulation and hard settling, a hard settling cake is formed that exhibits significant resistance to penetration, and such The slurry is not suitable for homogeneous slicing, cutting, grinding, lapping applications, and it is not possible to obtain the desired shape, surface quality, wafers or sliced disks consistently with uniform quality from larger ingots or bricks of hard material .

Example 5
The gel particles prepared and separated according to Example 2, step A were mixed with a sufficient amount of PEG 200 to obtain a wet gel particle concentration of ̃30% wt / wt. To this was added water and the carrier suspension was diluted to 25%, 50% and 75% respectively, to give three different dilutions each with three different gel particle concentrations. The overall pH, SSR and SVR variations for this example are shown in Table 5 below. According to another example herein, 18% zirconium oxide (ZrO ₂ ) was added to the mixture and the slurry properties were measured. The measurement results of the various dilutions are listed in the following table.

  The gel particles described here are in principle malleable or gelatinous particles. These particles are formed in-situ in the suspending medium or formed outside the final suspending medium, but in the latter case mixing, contacting or otherwise directly with the suspending medium Gelatinous that is ultimately suspended in the medium by causing interaction, physicochemical reaction, absorption interaction, electrostatic interaction or other "binding" mechanism between the gel particles and the suspension medium It is necessary to form malleable particles of

Example 6
A. Preparation of gel particles-
In this example, instead of using an aqueous solvent, a non-aqueous solvent using polyethylene glycol (PEG-200) was used. In addition, partially neutralized organic polymers are used as suspended gel particles instead of in-situ prepared metal hydroxides to produce suspended gel particles in non-aqueous PEG-200 solvent.

B. Preparation of Abrasive Particle Suspension Slurry- Suspension gel particles were formed by partial neutralization of a copolymer of acrylic acid and maleic acid with a final molecular weight of> 3000D. This polymer was first purchased as a 50/50 (wt / wt) aqueous solution and added to the suspension carrier PEG-200 to give a clear to slightly hazy solution of the copolymer acid. The polymeric acid is formed from the aminohydroxide base until appropriate gel particles are formed in the PEG suspension medium at a concentration sufficient to suspend about-47% of the SiC abrasive on a wt / wt basis. It was partially neutralized using. The main variables of this formulation, soft settling resistance (SSR) and suspension volume retention (SVR) data for non-aqueous slurries prepared as described above, are shown in Tables 6a and 1b below.

  It should be understood that gel particles are not considered emulsions, sols, or gels. Gel particles are "gelatinous" particles which are distinguished from one another. Formed as gelatinous particles in the medium using any of the above or other mechanisms, including the molecules of the liquid medium therein. The gel particles are partially solid but not in suspension as in the case of an emulsion. The gel particles utilized for the purposes of the present invention have common properties regardless of the chemical differences of the gel particles themselves or the mechanisms by which they are formed.

  The gel particles are formed by applying, performing, or using any means in the medium, but the resulting gel particles are separate and distinct molecules having different properties and distinct and independent from the whole medium and It has a physical structure. The gel particles are of a variety of different suspensions, using compounds, polymers, oligomers, organic or inorganic materials that do not have other similar properties to one another except for the typical properties utilized to form gel particles. It may be formed in a liquid or carrier medium.

In other words, the particles produced show similar properties even if the medium in which they are formed is different. Here are some examples:
1) Highly ionic organic suspended polymer particles that are very different physically, structurally, molecularly, and in terms of charge, from the glycol medium of PEG originally formed.
2) Very low ionic, inorganic suspended non-polymeric particles, which are very different physically, structurally, molecularly, and in terms of charge, from the water-based medium in which they were originally formed.
For the two previous examples, both are gel particles belonging to two very different "molecular species", but with similar formation steps listed below:
a) gel particles are prepared using the same method b) gel particles are prepared in-situ in the medium in which they are suspended c) gel particles are very different molecules of the medium in which they were produced D) gel particles are produced as distinct and different molecular environments present in the environment d) the density of the gel particles is somewhat greater than the density of the medium in which they were formed e) gel particles are physically interferent, density differences, ( Contribution of electrostatic charge in repulsion, and gel particles such as mechanical, secondary (ie intermolecular and intramolecular charge distribution effects (dipolar forces), hydrogen bonding forces or van der Waals forces) and inactivity Effect adhesion and / or physicochemical particle interference by particle interactions and effectively and effectively suspend inactive particles f) gel particles are formed in individually different in-situ media from which they are formed Chemical with another molecule They are prepared by interaction or for chemical reactions.

  These gel particles are very similar to one another and differ greatly from other forms of matter, regardless of what medium they are formed in or which components form the final gel particles. Have features or properties such as The gel particles are always formed in situ in a carrier medium having molecular, steric, rheological and physical properties distinct from the gel particles themselves. Even gel particles (eg, some polysaccharides) that are initially formed outside of the final carrier medium are exposed, interacted, mixed or reacted with the carrier at appropriate times to form the final gel particles. Thus, the final gel particles can be described as being formed in situ in the carrier medium. Because the gel particles contain in their structure part of the medium in which they are formed, they always have a somewhat higher density than the medium and tend to settle towards the bottom of the container over time. The gel particles formed are an environment which can be clearly distinguished physically, steric, structurally and visually from the medium in which they are formed. Gel particles are physical entities that have a measurable size and are separate from the carrier medium in which they are formed and suspended. Gel particles are malleable "soft" and flexible entities that mechanically adhere to other inert particles in the suspension medium to form some sort of cushion around the inert particles By doing this, the ability to suspend inert particles in the medium can be increased. The gel particles internally contain the molecules of the carrier medium in which they were formed. Although the size of the gel particles is "micro", the physical structure and size of the gel particles vary greatly in the range of 2-3 μm to 500 μm. Also, the size of the gel particles may be further increased depending on the size of the underlying molecule or polymer component being formed. The gel particles formed are not emulsions, sols, gels or soluble particles. The inside of the gel particles comprises the molecules of the carrier medium in which they are formed, but are semi-gelatinous particles which are distinguished from the carrier medium and which are different entities and environments than the carrier medium. Once formed, the gel particles do not react further with the medium in which they were formed. It contains carrier molecules inside but does not cause any further chemical reaction with the carrier medium. The gel particles of the present invention are not emulsions and can also be regarded as "semi-solid" particles that share solid particle, gel and emulsion properties together, but without defining emulsion properties. However, gel particles do not belong to any substance of these classes.

  Gel particles as suspended particles are predominantly present only under conditions where they are kept "wet" with the carrier molecules within the particles fully retained. Drying, or "evaporation", or removal of carrier particles from the gel particles impairs the suspension properties of the particles and the "dried" particles do not exhibit abrasive or inert particle suspension properties.

  There are numerous examples of gel particles that will satisfy the features and properties of the present invention. These substances available as gel particle materials can be classified into several groups having the following characteristics.

a) Alkaline earth metal hydroxides and oxides-hydrates, ie Mg (OH) ₂ , Mg 0-x H ₂ O)
b) Alkali neutralization salts of transition metals, using Bronsted or non-Bronsted bases in water or other corrosive media, Fe, Cr, Al, Zn, Cu, Ni, other formed in- Neutralized in-situ salts of substances where the final product in situ is the metal 'hydrated' or carrier impregnated hydroxide (also called hydrated oxide) c) Silicates, orthosilicates and certain Polysilicates d) Synthetic and natural modified starches such as corn starch
e) cellulose derivatives. Examples include, but are not limited to: hydroxycellulose, hydroxypropylcellulose, methylcarboxymethylcellulose, acetylcellulose f) Formed outside the suspension medium, but independent gelatinous by prolonged mixing with the suspension medium A polysaccharide that has been "ground" into particles and further ground into gel particles that can act as suspended particles and then resuspended in a carrier medium. The following are exemplified but not limited to: guar, guar gum, agar, agar-guar mixture, carrageenan, pectin, gellan gum, alginate and metal alginate (calcium alginate), plant-derived polysaccharides and mixtures of these materials g) Polyelectrolyte in a non-ionic polar organic carrier. This may include: sulfonated polystyrene (PSS), polyacrylic acid, methacrylic acid, maleic acid, or copolymers thereof (neutralized or partially neutralized) (PAA), ammonium poly (methacrylate) (APMA) , Polyesteramides and copolymers of the above polyamines, poly- (amino acids) polyelectrolytes (eg poly (L-aspartic acid) (PAA), poly (L-glutamic acid), (PGA) and poly (L-lysine) (PLL) ).
All gel particles for use in connection with the present invention have common properties and characteristics regardless of formation mechanism or origin, as well as many common properties, behaviors and a wide variety of structures, compounds, polymers and materials Have a characteristic thread that ties the Regardless of formation mechanism or origin, all "gel particles" defined and described in the above examples have the same common performance and behavior characteristics, which are required for the above useful applications It is.

  Polysaccharides have been used as coating compositions in aqueous carriers. In one example of the formation of such a coating composition, modified polysaccharides are prepared by first suspending 5 g of selected pure polysaccharides (agar and guar gum) in 100 ml of distilled water. The suspension was stirred at 500 rpm for 24 hours using a magnetic stirrer. The resulting swollen mass was spread on an enamel tray and dried at 40 ° C. for 72 hours. The dried product was scraped out of the tray and ground in a glass pestle mortar to obtain coarse non-free flowing heterogeneous particles of treated polysaccharide (treated agar and treated guar gum). The treated polysaccharide is then co-ground in a glass pestle mortar for 20 minutes with mannitol in a 1: 1 ratio and then passed through a # 22 sieve to obtain modified polysaccharide (co-ground agar and co-ground guar gum) I got The resulting product was then used as a gelatinous coating for pharmaceuticals for human consumption. While this example can produce gel particles by other means than simply mixing the appropriate composition into the liquid carrier, it also retains the properties and features described with respect to the present invention. Suggest.

  The polysaccharide also prevents the collapse of the ditch inwards and builds a structural wall alternative to the conventional thickening water used to maintain the open ditch while preventing water from migrating into the soil. It has also been used to form helping gelatinous particles. The addition of polysaccharides with appropriate viscosity and solvating properties such as starch, guar, carboxymethylcellulose, sugar beet pulp derivatives and hydroethylcellulose to water produced a thickened gelatinous slurry with slow conversion to solution. It has been found that polysaccharide polymers, when added to water as a powder or in the form of an oily slurry, require long solvation times in both cases. This is an example of how different polymers can be utilized, either in powder or organic slurry form, to form gel particles for use in the main carrier system.

  Polyelectrolytes are "dipolar" charged polymers that can stabilize (or destabilize) colloidal emulsions through electrostatic interactions. The effectiveness of polyelectrolytes depends on molecular weight, pH, solvent polarity, ionic strength, and the hydrophilic-lipophilic balance. The polyelectrolyte consists of positively or negatively charged repeat units. The polyelectrolyte is charged by dissociation of the monomer side groups. As more of the monomer side groups disassociate, the resulting charge is greater. Polyelectrolytes are classified as positive (cations) or negative (anions) according to the charge of the polymer. The thickness of the polyelectrolyte layer is determined by the level of charge of the polyelectrolyte and the ionic strength. Some examples of useful polyelectrolytes are listed above.

Example 7
In order to maintain the separation between the gel particles and the added abrasive or inert particles, the gel-particle distribution in the carrier system also needs to be addressed. A test was constructed to determine if gel particle dilution changes the effectiveness of the gel particles to prevent aggregation of the added abrasive or inert particles in the slurry. The formation of gel particles in a water based aqueous solution was prepared. All tests were performed at room temperature of 22 ° C. in aliquots of 40 ml regardless of dilution. Table 7 below shows the dilution factor and suspension volume retention [SVR] expressed as% of the original suspension volume of 40 ml in a calibrated container.

  A reduction of SVR over time is only possible if the gel particle density is greater than the density of the medium in which it is suspended. Regardless of the dilution level of the gel particle slurry, the SVR values of all samples decreased with time, indicating that the density of gel particles and suspended particles is greater than the density of the aqueous suspension medium. In fact, for all gel particle dilution levels, the largest "soft settling" of gel particles and suspended particles occurs in the first 24 hours.

  The preceding examples do not mean to be comprehensive or complete at all, but share the common performance and behavior characteristics of the unique "inert particle stabilization / suspension" indicator, and any material that meets the above-mentioned properties , Compatible with materials, compounds, polymers (organic, organometallic or inorganic physical properties). All of these diverse materials are common, but necessary for long-term stabilization of other inert particles that would otherwise settle to the bottom of the vessel as a rigid or solidified agglomerated cake It has unique properties and can be taken simply as an illustration of the concept of simply the same unique "gel particle".

  Thus, the origin of the gel particle, the nature of the compound used for the formation, the nature of the particular component of the material or polymer, the structure is an organic, metal-organic or inorganic structure, the carrier system in which the gel particle is present is organic Regardless of whether they are inorganic, inorganic or composites, all of the series of components described are of the same type of unique form having the properties and characteristics necessary to act as suspended particles in a carrier medium or system. It is a diverse example of gelatinous material.

  The present invention can be practiced in other specific forms without departing from the spirit or main features thereof, and thus the described embodiments are illustrative and non-restrictive in every respect, and the scope of the present invention Rather than the preceding detailed description, it should be construed that the appended claims are intended to cover all such modifications as fall within the scope of equivalents.

Claims (18)

  Unlike inert particles, which cause sufficient interference to the sedimentation of inert particles in the carrier medium, in-situ formation of suspended particles in the pH 4 to 12 range while including the carrier medium in the carrier medium Inert particles in order to contain suspended particles selected from the group consisting of possible alkaline earth metal and transition metal hydroxides, oxyhydroxides and oxide hydrates in the range of 0.1 to 60% by weight Inert colloidal or non-colloidal abrasive or stable aqueous of non-abrasive inert particles, including producing suspended particles formed in-situ for the purpose of establishing suspended particles of appropriate concentration Method of suspension in a semi-aqueous or organic carrier medium, having a structurally different molecular, steric, rheological and physical structure significantly different from the carrier medium, with a density greater than that of the carrier medium, visually the carrier medium Identified to While showing possible differences in the physical structure, a measurable size difference in the range of about 2-3 μm to 500 μm, the suspended particles comprise molecules of the carrier formed, but the ability to cause further reaction with the carrier medium is In-situ formation of suspended particles in a carrier medium that results in suspended particles exhibiting substantially uniform properties that are independent of the formation mechanism or origin of the components, thereby suspending and inactive particles and Force between suspended particles and inert particles to realize the distance between them causing physical interference, chemical, physical or physicochemical interference, and electrostatic charge on the inactive particles of the suspended particles or itself Prevention of aggregation or coagulation of the inert particles in the carrier medium over a long period of time by suspending the inert particles in the carrier medium with at least one of repulsions.   The method of claim 1, wherein the suspended particles are formed in a medium separate from the final carrier medium.   The method of claim 1, wherein the aqueous carrier medium contains at least one inert polar solvent.   4. The inert polar solvent according to claim 3, wherein the inert polar solvent is selected from the group consisting of dialkylene glycol, alkylene glycol, glycol ether, polyalkylene glycol, alkyl lactone, N-methyl pyrrolidone, alkylene carbonate, acetonitrile, and dimethyl acetamide. the method of.   The suspended particles are gel particles, sol-gel particles, and gelatinous precipitates formed from hydroxides, oxyhydroxides, or oxide hydrates of alkaline earth metals or transition metals. The method described in.   The suspended particles are formed of one selected from the group consisting of aluminum hydroxide, aluminum oxyhydroxide, zinc hydroxide, copper hydroxide, magnesium hydroxide and tin hydroxide. Method.   Said suspended particles are Fe, Cr, Al, Zn, Cu, Ni neutralized in situ with Bronsted or non-Bronsted base from alkali neutralized salts of transition metals formed in aqueous or caustic media. The method according to claim 1, wherein the gel particles, the sol gel particles, and the gelatin precipitate formed from the above, and the suspended particles are hydrated oxides of metal.   2. The method according to claim 1, wherein the suspended particles are modified starch, or gel particles, sol gel particles, and gelatinous precipitates formed from a cellulose derivative including hydroxyl cellulose, hydroxyl propyl cellulose, methyl carboxymethyl cellulose and acetyl cellulose. the method of.   Said suspended particles are formed from a polysaccharide formed outside of a carrier medium comprising guar, guar gum, agar, agar-guar mixture, carrageenan, pectin, gellan gum, alginate, metal alginate, plant derived polysaccharide and mixtures thereof The method according to claim 1, which is formed gel particles, sol gel particles and gelatinous precipitates.   Non-ionic said suspension particles comprising sulfonated polystyrene, polyacrylic acid, methacrylic acid, maleic acid or copolymers thereof, ammonium poly (methacrylate), copolymers of polyesteramides and polyamines, and poly- (amino acid) polyelectrolytes The method of claim 1, wherein the gel particles, the sol-gel particles, the gelatinous precipitate are formed from a polyelectrolyte formed in a polar or polar carrier medium.   Said inert particles suspended are selected from the group consisting of titanium dioxide, silicon carbide, zirconium oxide, silica, cerium oxide, aluminum oxide, silicon nitride, boron carbide, tungsten carbide, diamond, silicon dioxide and dry pigment particles The method of claim 1, wherein   The method of claim 1 comprising a corrosion inhibitor.   The method according to claim 1, comprising using an inert salt to provide an additional density difference or electrostatic repulsion between the suspended particles and the inert particles.   14. A method according to claim 13, comprising the removal of inert salts produced by the formation of suspended particles.   Suspension gel particles formed in-situ in a stable aqueous, semi-aqueous or organic carrier medium to suspend the inert colloidal or non-colloidal abrasive or non-abrasive inert particles in a stable carrier medium, The carrier medium is included in the range of 0.1 to 60% by weight different from the inert particle, thereby establishing the appropriate concentration of suspended particles to the inert particle to establish in the carrier medium of the inert particle Alkaline earth metal and transition metal forming in-situ the suspended particles while including the carrier medium in the carrier medium in the range of pH 4 to 12, said suspended gel particles causing sufficient interference to the sedimentation of Said suspended gel particles selected from the group consisting of hydroxides, oxyhydroxides and oxide hydrates, molecular, steric, rheological and physical significantly different from the carrier medium The structure has a density greater than the density of the carrier medium, the carrier medium is another physical structure visually distinguishable, and the difference in size that can be measured in the range of about 2-3 μm to 500 μm, and suspended gel The particles contain molecules of the carrier formed but are not capable of undergoing further reaction with the carrier medium, resulting in a suspended gel particle exhibiting substantially uniform properties that is independent of the formation mechanism or origin of the component Suspended gel particles that provide in-situ formation of suspended particles in a carrier medium, thereby resulting in physical, chemical, physical or physicochemical interference between suspended particles and inactive particles For a long period of time by the suspension of inert particles in the carrier medium with at least one of the attraction between the particles and the inert particles, and the electrostatic charge repulsion against the inert particles of the suspension gel particles or themselves. Agglomeration or prevention of coagulation of the inert particles of Wataru in the carrier medium.   Mechanically adhering to any of the inert particles in the carrier medium as a malleable flexible physical entity independent of the carrier medium to form a cushion around the inert particles, 16. Suspension gel particles according to claim 15, which can be used to increase the suspension of inert particles.   16. The suspended gel particle of claim 15, wherein the gel particle remains present only under conditions such that the carrier molecules in the gel particle remain semi-liquid with intact.   Alkaline earth metal hydroxides and oxide hydrates, alkali neutralized salts of transition metals, silicates, orthosilicates and certain polysilicates, modified starches, cellulose derivatives, polysaccharides, nonionic polar organics 16. The suspension gel particle of claim 15, having a component chemical compound selected from the group consisting of polyelectrolytes in a carrier.