CN1798967A - Methods of specifying or identifying particulate material - Google Patents

Abstract

This invention relates to methods for specifying the quantity, batch, or shipment of granular materials, including using at least one interfacial potential property value to specify the quantity, batch, or shipment of the granular materials. The invention also relates to methods for indicating the grade, type, and/or brand of granular materials. At least one morphological and/or chemical value may also be included. These values may be included in the product specification.

Description

Methods of specifying or identifying granular materials

Pursuant to 35 U.S.C.ξ120, this application claims priority to U.S. Patent Application 10/650,124, filed August 27, 2003, which claims priority to the U.S. earlier provisional application, filed April 1, 2003, pursuant to 35 U.S.C.ξ119(e) Priority of patent applications 60/459230, 60/485964 filed July 10, 2003, and 60/491632, filed July 31, 2003. These applications are incorporated herein by reference.

Technical field

The present invention relates to a method of providing product specifications for granular materials. The present invention also relates to a method of labeling, promoting or representing the grade, type and/or brand of granular material based on the value of the interface potential. The invention also relates to a method of specifying batches, batches or shipments of granular material based on interfacial potential values.

Background technique

Chemical industry products are generally one of two types - formula chemical products and performance chemical products. A chemical product is defined by its composition. If sold in different grades, the grades are distinguished by impurity concentration. Examples thereof include ammonia, benzene, carbon tetrachloride, diethyl ether and formaldehyde. Performance chemical products, including polymers, dyes, pigments, and fragrances, are valued not for what they are made of, but for what they can do. Important classes of performance chemical products include fine-grained products such as carbon black, silica, titanium dioxide, tantalum, and calcium carbonate, which are used in areas including reinforcement, rheology, dyeing, and electrical conductivity.

Fine particles are used to improve the properties of composite materials, such as rheology, flow, strength, color, etc. The ability of fine-grained products to achieve the desired level of performance depends on the particle characteristics. To distinguish performance levels, types or classes are usually defined. These definitions include designating certain particle properties and assigning typical or target values to those properties. Prior to the present invention, particle properties were related to morphology, such as particle size, particle size distribution, particle shape or structure, and the like.

To ensure consistency, develop instructions for fine-grained products. These specifications typically include one or more morphological measures and may also include one or more chemical compositional measures. Common measures of morphology are particle size, surface area, structure, porosity, aggregate size, and aggregate shape. Common measurements of chemicals include bulk and surface composition and analytical values for extractables. Variability in these properties can be measured during production to ensure that the process is in control (often referred to as quality control or QC), or on the product prior to shipment (often referred to as quality assurance or QA) .

For example, carbon black is generally sold with at least one morphological specification, which can be surface area, particle size, structure and porosity. Performance tests such as bonded rubber or combined moisture absorption (CMA) tests can also be performed, depending on the intended use of the carbon black. However, these are generally not included on product specification sheets.

Despite these quality control and quality assurance (QC/QA) efforts, users often complain of receiving batches that do not perform as expected, even though the products are "within specification." For example, variations in the rate of rubber cure, the appearance of white haze spots on molded rubber parts, the low thixotropy of the binder, and the number of plastic recombinations have all been traced to batch-to-batch variations in carbon black, even though each batch was within specification. within range. This usually results in an intensive and costly study of the process and product by the manufacturer and adjustments made as far as possible so that the product can once again have the desired properties.

Determining why a product does not have the desired performance is ineffective and often a waste of time and money. It involves evaluating why a problem occurred, rather than avoiding it in the first place. The manufacturer will adjust the production steps many times, not to understand the result, but just to try to change the product, to somehow see the difference in the product. Sometimes it's actually guess work.

Accordingly, there is a need, particularly in the granular materials industry, for better methods of specifying batches, batches and/or shipments of granular materials and methods of assigning or identifying the type, grade and/or brand of granular materials.

Contents of the invention

The present invention relates in part to a method of creating a product specification for a lot, batch or shipment of granular material, which involves specifying interfacial potential energy values for the batch, batch or shipment of granular material. Interfacial potential values may be included on the product specification sheet for the brand or grade of granular material. At least one morphological and/or chemical value may also be specified, which may also be included on the product specification sheet.

The invention also relates to a method of identifying or representing a grade, brand or type of granular material by assigning or providing at least one interfacial potential performance value for the grade, brand or type of granular material. At least one morphological and/or chemical value can also be assigned.

The invention also relates to a method for a granular manufacturer to provide granular material to a user, comprising the step of specifying at least one interfacial potential value for the grade, brand or type of granular material. It is also possible to mark at least one morphological and/or chemical value on the granular material.

The invention also relates to a method of ordering granular material comprising the step of ordering the granular material by specifying at least one specified interface potential value. Interfacial potential values for granular materials may be requested by the user and/or manufacturer prior to or at the time of ordering. At least one morphological and/or chemical value can also be specified for the granular material.

The present invention also relates to a method for improving the identification of batches, batches or shipments of granular material comprising updating existing specifications for batches, batches or shipments of granular material by adding or specifying at least one interfacial potential value A step of. It is also possible to add at least one morphological and/or chemical value for illustration to the existing description.

The present invention also relates to a method of improving the identification of a grade, type or brand of granular material comprising updating an existing grade, type or brand of granular material by indicating or representing at least one interfacial potential value for the grade, type or brand of granular material Or the steps in the brand's instructions.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the scope of the invention as defined by the claims.

Description of drawings

Figure 1 shows the maximum torque versus volume for the same grade of carbon black using different probe liquids.

Detailed ways

The present invention relates to a method of creating a product specification for a lot, lot or shipment of granular material. The invention also relates to methods of identifying or indicating the grade, brand or type of granular material. The invention also relates to a method of doing business with customers using product instructions. The method of the present invention comprises the use of at least one interface potential value by which a certain lot, lot or shipment can be claimed and/or a particular grade, brand or type of granular material provided for a certain lot, lot or shipment . The invention also relates to a product specification for a batch, batch or shipment of granular material comprising at least one interfacial potential value. For the purposes of the invention, the term "value" as used herein includes a specific number or value or a plurality of numbers or values or a range of such numbers or values.

Granular materials such as fillers and pigments are manufactured within defined specifications, and even then we find that the products sometimes do not perform consistently when used by the user. The reasons for the inability of products to exhibit consistent performance even within the morphological specifications are not fully understood by the industry to date. The present invention can now specify batches, batches or shipments of granular material based on at least one interface potential value, making it easier for users to achieve the desired properties of their products. This method can be used to provide users with products that perform consistently across their end products. The present invention also provides a method of better identifying or representing the type, grade and/or brand of granular product. The system enables producers and users to better describe the type, grade and/or brand of granular products and enables industry personnel to more precisely promote the type, grade and/or brand of granular products.

Granular materials can be produced in a variety of units, including batches, batches, samples, shipments, and more. Generally speaking, the user and/or supplier agrees to label the unit of the product, which can be included in the contract, and the contract includes oral agreement, purchase order, delivery note, contract, waiver agreement, or a combination thereof. The method of the invention involves specifying at least one interfacial potential value for a batch, batch and/or shipment of granular material. Lots, batches, and/or shipments can be in any quantity, for example, from a very small test sample to a large order of railcars or larger quantities. The method of the invention may also comprise specifying at least one morphological value and/or at least one chemical value for a lot, batch, sample and/or shipment of granular material. Each or some of these values may be included on the product specification sheet.

The invention also relates to methods of promoting, representing or in some way identifying the brand, grade or type of granular material. The method includes naming, annotating, designating, enumerating, characterizing, or assigning at least one interfacial potential value to a brand, grade, or type of granular material. At least one morphological and/or chemical value may also be included. The industry sometimes refers to this as the "typical value" for the product. As used herein, reference to granular material includes any means of identifying the material.

Particulate materials are used in various compounding systems including, for example, dispersions in elastomers, polymers, solvents, resins, or mixtures thereof. Important aspects of performance include reinforcement, rheology control, penetration network formation, dispersion, color and conductivity. The performance of these composite systems derives in part from the morphology of the granular materials used. Other physical phenomena involving granular materials can respond to interfacial potential properties. Some phenomena also respond to a combination of the two. Because interfacial potential and morphology play an important role in granular materials, the method of the present invention includes assigning at least one interfacial potential-related property to granular materials. We surprisingly found that better characterization and better recognition, especially for users, can be achieved with this approach. Such instructions also allow for better quality assurance (QA) and quality control (QC).

The interfacial potential of a granular material is defined by a measure of the physical phenomenon that depends on the interaction of the granular material with other materials or with itself after removing the influence of morphology. When two particles are in contact with each other, the interfacial potential is the cohesion per unit contact area. When granular materials are mixed into a fluid, the interfacial potential is the bond per particle area. If the measure is per unit mass, then the overall interaction depends on the surface area per unit mass and the interfacial potential per unit area.

Examples of phenomena that are only related to interfacial potentials include partitioning of particles between liquid phases, expansion pressure of adsorbed gases, and droplet contact angles. These phenomena can be measured, and there is no ambiguity as to whether the results are derived from morphology or from the interface potential, since they depend only on the interface potential.

But as mentioned above, many useful physical phenomena respond to both morphology and interfacial potential. The morphology of a granular material is the description of its shape, size and structure. Morphology can include particle size, surface area, particle porosity, aggregate size, aggregate shape, maximum packing density, powder bed porosity. Morphology can also include particle size, pore size, aggregate size, etc. Distribution properties of these values such as mean, standard deviation, width, skewness, etc. Morphological values are the result of measuring one or a combination of these properties. Surface area per unit mass, diffusion constant of individual particles, mean diameter of primary particles and microstructures such as diameter, shape and number of pores are examples of morphological values.

Examples of phenomena that respond to both morphology and interfacial potential include aspects of rheology (e.g., yield, viscosity, and shear thinning), wicking rates of fluids in a powder column, and wetting under agitation. Maximum torque and fluid volume occurring in wet powder (ie, absorptometer or oil absorption test). For example, the ascent rate of a fluid in a column of packed particles depends both on the pore size distribution of the column and on the strength of the wetting interaction per unit area between the fluid and the particle surface. The volume at which maximum torque is generated depends on the maximum density the powder can be packed and the strength of the capillary forces when squeezing the powder. The capillary force depends on the size of the hole and the interface potential per unit area. If the interactions are large enough and/or the pores are small enough, the granular material can be extruded to or near its maximum density. Therefore, for absorption measurements with some liquids on some granular materials, only particle morphology is used to determine the characteristic volume. For other liquids, volume and torque are determined using morphology and interfacial potential.

When these phenomena due to morphology and interfacial potential arise, the method of analyzing these measurements, ie the calculation method or algorithm used will determine whether it is the morphological value or the interfacial potential performance value. It is thus possible to use experiments that respond to both morphology and interfacial potential, obtaining independent information on both.

For example, a subset of physical phenomena that respond to both morphology and interface potential are those for which the relevant aspect of morphology is only surface area and the dependence on area is known. Typical examples of this phenomenon are adsorption studies to determine the partitioning of trace molecules between the surface and the gas or liquid phase. For these physical phenomena, the measured values of the surface area and the calculated interfacial potential are adjusted.

Another subset of physical phenomena that respond to both morphology and interfacial potential are phenomena for which the dependence on morphology and interfacial potential can be separated by mathematical analysis. For example, the amount of gas adsorbed as a function of pressure depends on the surface area and interfacial potential. The surface area or interfacial potential can be calculated using this function and known gas molecular sizes. Calculating the surface area with nitrogen is the so-called BET method. The usual calculation can get the surface area, which is an aspect of morphology, and the method is morphological method. Different calculations get the interface potential, so such a method is the interface potential method.

Some physical phenomena can be divided algorithmically into morphological effects and interface potentials. This provides the basis for measuring morphology or interfacial potentials. The algorithm that interprets the data determines the type of measure.

Phenomena responsive to both morphology and interfacial potential can be used to assign interfacial potential energy values to granular materials if one of the following conditions is met.

A) If inert probes can be used to measure physical phenomena while eliminating morphological effects. Inert probes are probes for which the interface potential can be ignored. For example, in reversed-phase gas chromatography (IGC), the residence time of an inert probe is also measured.

B) If an external parameter such as pressure or temperature is changed, the response to this parameter can be independently calculated for one or more morphological and interfacial potential values. For example, BET analysis records the amount adsorbed as a function of pressure, and two constants are calculated from these data. One constant measures the surface area and one constant measures the interface potential.

C) If the physical phenomenon is tested in a different fluid with the same granular material. These results were compared to determine differences when the morphology of the particles was the same. For example, the wicking rates of various liquids can be compared to the wicking rates of hydrocarbons through a similarly packed powder bed.

D) If the number of different trials responding to both the morphology and the interface potential is greater than the number of relevant morphological parameters minus the number determined by independent trials, then there are a sufficient number of independent trials to guarantee the consistency of the morphological parameters, plus At least one aspect of the upper interface potential.

In all these conditions, except D), the common aim is to identify the part of the physical phenomenon that depends on the interaction of the granular material with other materials or with itself after removing the influence of morphology. This part is the interface potential.

Therefore, in the method of the present invention, the step of specifying or assigning at least one interface potential performance value may utilize or include any one of the above-mentioned techniques. Other techniques are detailed below.

As mentioned above, the method of the invention may further comprise the step of specifying at least one morphological value. Morphological and interfacial potential values may be included on product specification sheets. Morphological values can also be included on product literature (catalogues, brochures, advertisements, promotions, web sites and other newspaper and electronic media). Morphological values can be any of the above and can be determined by any method known in the art, such as colloidal techniques, including liquid or vapor adsorption, microscopy or combinations thereof. Common liquid or vapor probes used for adsorption include nitrogen, iodine, cetyltrimethylammonium bromide (CTAB), dibutylphthalate (DBP), or paraffin oil. Examples of useful microscopy techniques include, but are not limited to, Transmission Electron Microscopy (TEM), X-ray Diffraction, Dark Field Microscopy, Oxidation Studies, Diffraction Beam Electron Microscopy, Phase Contrast Transmission Electron Microscopy Scanning Electron Microscopy (SEM), Scanning Tunneling Electron Microscopy (STEM), Scanning Tunneling Microscopy (STM), Scanning Force Microscopy (SFM), Atomic Force Microscopy (AFM) Imaging . Examples of colloidal technologies include, but are not limited to, multi-shade (black or colored), coloring power (ASTM D 3265) and nitrogen adsorption data (ASTM D 3037), cetyltrimethylammonium bromide (ASTM D 3765) or Iodine (ASTM D 1510). The amount and type of porosity and the chemical nature of the surface of the particulate material can affect the surface area obtained by any of the above methods in different ways. Porosity can be estimated from the apparent excess surface area detected in the adsorption of a small probe, such as nitrogen, on a large probe, such as CTAB. Aggregate size can be estimated using TEM, disc centrifugal photodeposition, deposition field flow fractionation, capillary hydraulic fractionation, dynamic light dispersion, and differential mobility. Aggregate shape can be estimated from oil adsorption, especially DBP, and specific volume can be estimated from density-pressure curves and TEM.

Examples of morphological properties and the tests used to measure them are shown in Table 1 below. These morphological values can be used alone, or in combination with other morphological values.

Table 1 Morphological properties experiment method Particle Size and Particle Size Distribution Surface Area Computation for Multitone in Transmission Electron Microscopy (TEM) surface area Nitrogen Adsorption (ASTM D 3037) Iodine Adsorption (ASTM 1510) CTAB Adsorption (ASTM D 3765) Carman Surface Area Pore Size and Distribution Difference Between Nitrogen and CTAB Surface Area Aggregate size and distribution TEM Light Dispersing Disk Centrifugal aggregate shape TEM Oil Adsorption DBP Absorption Technology Obtains Specific Volume from Density-Pressure Curve

The methods of the invention may also include the step of specifying or assigning at least one chemical value in various embodiments of the invention. Chemical and interfacial potential values and/or morphological values may also be included on product specification sheets. The chemical properties of the granular material are the bulk (or bulk) composition of the material, surface composition and/or extractable material. The type, quantity and distribution of chemical moieties on the surface are called surface chemistry. For example, the surface of the carbon black can include carbon-oxygen surface groups, carbon-hydrogen surface groups, and/or other substituted carbon groups.

The chemical value of the particulate material can be determined using any technique known in the art. For example, desorption (e.g. desorption of oxygen groups on carbon black), neutralization of surface groups with acids and bases, potentiometric, temperature and radiometric titrations, electrokinetic tests, direct analysis with specific chemical reactions, extreme Spectroscopy, infrared spectroscopy (IR) and X-ray photoelectron spectroscopy (XPS) measure the amount of chemical moieties. Surface chemistry can be altered by chemical reactions and by removal of extractable materials. Examples of chemical values include, but are not limited to, pH, amount of functional groups, and zeta potential.

We have found that, in general, neither measuring chemical composition nor measuring morphology is sufficient to effectively characterize granular materials to provide greater consistency in the end product. The surface of granular materials can contain a large number of different types of chemical species, so too many species need to be identified and their relative positions on the surface to be effectively described. Additionally, although qualitative and quantitative analysis methods exist, location localization is beyond the current state of the art.

For the process of the invention any particulate material may be used. The granular material can be in any form such as powder, pellets or fluff material. Examples of particulate materials include, but are not limited to, fillers, extenders, carbonaceous materials, carbon black, inorganic salts, silica (such as fumed silica, precipitated silica, or colloidal silica), silica Aerogels, fumed oxides, silicates, silica sols including Stéber sols, metal oxides, hydrated metal oxides, iron oxides, aluminum oxides, boehmite, aluminum silicates, clays , Kaolin, Yongshi, montmorillonite, attapulgite, zeolite, ceramics (such as: metal carbide, metal nitride or metal boride), calcium carbonate, limestone, barium sulfate, diatomaceous earth, talc, pigment ( Such as: phthalocyanine pigments, Prussian blue, chromium oxide and chrome green), zinc sulfide, zinc oxide, titanium dioxide, antimony oxide, lead zinc, metals (such as tantalum, niobium, iron, aluminum or silicon), surface-treated Arbitrary substances such as hydrophobic silicas, surface modified carbon blacks, polymer treated powders and lake pigments. Combinations or mixtures of these particulate materials may also be used. Examples of carbonaceous materials include, but are not limited to, carbon black, graphite, glassy carbon, activated carbon, carbon fiber, nanotubes, graphite, and the like. Other examples include aggregates comprising a carbon phase and a silicon-containing species phase or aggregates comprising a carbon phase and a metal-containing species phase. Additionally, coated particulate materials such as silica coated carbon black are other examples of particulate materials. In addition, carbonaceous materials or other particulate materials may be modified by any method such as incidental organic groups, polymer groups, and the like. Examples include those described in the following U.S. Patents: 5,747,562, 5,830,930, 5,877,238, 5,904,762, 5,916,934, 5,919,841, 5,948,835, 6,008,272, 6,017,980, 6,028,137, 6,057,387, 6,197,274, 6,211,279, 6,323,493, 68 incorporated herein 49 Patent as a reference.

As noted above, the interfacial potential property value may be any property that can be associated with the interfacial potential of the granular material. In order to achieve the purpose of the present invention, as detailed below, the test results can be used to determine the interface potential, or allow a method to assign values to the granular material itself or to the grade or brand of the granular material, and the test results are affected by the granular material interface. In the present invention, it can be considered that the test result is the value of the interface potential. These values can be determined using various techniques known in the art including the following techniques:

Interfacial Potential Determination with Multitone. The optical density of a granular material such as a pigment in a matrix depends on its intrinsic properties and how well the granular material is dispersed throughout the matrix. If the dispersion is poor, the optical density is low. If the dispersion is good, the optical density is high. The dispersibility of a granular material depends both on its morphology and on its interfacial potential. Thus, multi-hue depends on the interfacial potential of the pigment. For the same granular material dispersed in different matrices under the same conditions, the difference in polytone can be used as a specification for the interfacial potential of the granular filler.

The interfacial potential was determined using the gas adsorption technique. Some of the above methods for determining surface area using gas adsorption, such as BET analysis, fit the data to two parameters - one for the surface area and one for the solid-gas interaction. The parameter used for solid-gas interactions is a measure of the interfacial potential. Therefore, information about the interfacial potential can be learned from the same data used to report surface area by BET analysis. Therefore, methods involving the measurement of adsorption of gases other than nitrogen and krypton, the common "inert" gases used in BET analysis, can be used to determine the interfacial potential. Examples of alternative gases that can be used to measure interfacial potential include water, ammonia, and various organic vapors such as toluene, ethanol, etc. The preferred gas adsorption technique and data analysis method to obtain the interfacial potential is to measure the expansion pressure, which will be detailed below.

The interfacial potential was determined by adsorption from solution. Adsorption from solution is a technique similar to gas adsorption. Many solutes are surface active, that is, when they are mixed into a solution, they accumulate preferentially at the surface of the particulate material. The amount adsorbed depends on the surface area, morphology and interfacial potential. If the adsorption of two or more solutes of different surface activity is measured on the same granular material, enough information can be gathered that they respond independently to morphology and interfacial potential to be useful as a measure of interfacial potential .

The interfacial potential is determined by light dispersion or disc centrifugation. In order to obtain aggregate size through light dispersion, the granular material must be highly diluted in the liquid. Surfactants are usually added to ensure good separation of the granular material, no flocculation during the measurement, and accurate measurement of its size. This experimental deviation will give information on the interfacial potential, especially on the cohesion of granular materials. For this method, the particle size is measured as a function of time in the absence of surfactant. Dispersions, even highly diluted, will flocculate over time. The rate of flocculation is a measure of the cohesion of granular material. Thus, a measure of particle size or particle size distribution as a function of time is a measure of interfacial potential, especially cohesion.

The interfacial potential was determined by the oil adsorption method. A common type of QA/QC test for granular materials such as carbon black structures is to slowly add liquid to a stirred bulk material. As the ratio of liquid volume to mass of granular material increases, the torque required for mixing changes. Generally, the ratio of liquid added to mass of material at maximum torque is reported for QA/QC testing of structures and can appear on product specification sheets.

Another QA/QC test is to report the same ratio at a predetermined ratio of maximum torque. The preferred liquid is dibutyl phthalate (DBP) and the reported value is often referred to as the DBP number. Paraffin oil is also used. These volume to mass ratios are a strong function of the morphology of the granular material.

However, the mobility of granular materials wetted by liquids also depends on the interfacial potential across the relative strengths of particle-particle interactions and particle-liquid interactions. When the adsorption test was repeated with a second liquid on the same granular material, the relationship between torque and volume of added liquid changed. For example, the maximum torque may be different for the same granular material in different liquids, or in other words, different volumes of liquid are added to achieve the maximum torque. These differences reflect the interfacial potential of the granular material. Therefore, a combination of oil sorption tests performed with different liquids can be used to specify the interfacial potential of granular materials.

The interfacial potential was determined by the wicking rate. When granular material is packed in the column and the bottom of the packed bed comes into contact with liquid, the liquid is drawn up through the packed bed. The wicking rate depends on the packing of the granular material (which depends on the morphology) and the strength of the interaction between the granular material and the liquid (which depends on the interfacial potential). A comparative relationship of the wicking rates of two or more liquids within equal packed columns of the same granular material can be used as a measure of the interfacial potential of the granular material.

The interfacial potential was determined by rheological tests. The degree of flocculation of granular materials in liquid depends on the balance between particle-particle interaction and particle-liquid interaction. In other words, the degree of flocculation depends on the interfacial potential of the granular material. One measure of this balance is shear thinning - the decrease in viscosity with increasing shear rate. Another measure of the degree of flocculation is the Bingham yield point. A further measure of the degree of flocculation is the modulus of elasticity at low stress. Each of these methods can be used to determine the interfacial potential of granular materials.

The interfacial potential was determined by sedimentation volume. When the dispersion is flocculated, the particles settle due to the increase in size. If the particle-particle energy is greater than the particle-liquid capacity, the flocs are large and the sedimentation height is high. Therefore, a measure of the settling height of a flocculated dispersion of granular material can be used as a measure of the interfacial potential.

The interfacial potential was determined by the phase separation method. When granular material is added to a vessel with two or more immiscible liquids, the material preferentially accumulates in one of the phases or at a phase boundary. The origin of this preferential segregation is due to the interfacial potential of the granular material and thus can be used as a specification for the granular material.

The interfacial potential was determined by reversed-phase gas chromatography. Inverted-phase gas chromatography (IGC) is used to measure the residence time of a gas probe flowing through a packed bed of granular material. The stronger the interface potential, the longer the residence time. Residence time also depends on the morphology and packing of the granular material. Therefore, in a general procedure, the residence time of organic vapors is compared to that of hydrocarbons. This analysis provides a measure of the interfacial potential of the granular material and thus can be used as a method of specifying the granular material.

The interfacial potential is determined by dilation pressure. The expansion pressure of a gas on a granular material is a measure of the interfacial potential. The expansion pressure (number of moles as a function of gas partial pressure) can be calculated from the gas adsorption isotherm. The expansion pressure is the integral of the adsorption curve when the partial pressure is plotted logarithmically. If data are reported as moles adsorbed per unit mass, expansion pressure is energy per unit mass. The calculated expansion pressure can be divided by the specific surface area to obtain the interface potential in units of energy per unit area. Various gases can be used including, for example, tetrahydrofuran, water, ethanol, toluene, methyl ethyl ketone, cyclohexanone, and the like. Calculating the expansion pressure of the granular material for each gas provides a measure of the interfacial potential.

Other methods of determining the interfacial potential of particulate materials can be used and are known to those of ordinary skill in the art. Examples include:

a) extruding the granular material to obtain a flat surface on which the contact angle of the probe liquid is measured;

b) measuring the gas pressure, removing the probe liquid from the pores of the packed bed of granular material after filling or partially filling with liquid;

c) measuring the centrifugal force necessary to submerge particles of granular material floating on the probe liquid;

d) measuring the two-dimensional pressure sufficient to force particles of granular material floating on the probe liquid into a Langmuir cell;

e) measuring the relative adsorption amount of the dye probe;

f) measuring the heat of the granular material when submerged in the probe liquid;

g) Measure the heat released when the granular material adsorbs the sample to be adsorbed. This can be done in a flow calorimeter with the adsorbate dissolved in the carrier liquid, or in a batch calorimeter where the adsorbate is a pure liquid or solution;

h) Measurement of sedimentation volume in a homologous series of test liquids as described by Morrison, I.D.; Ross, S. Colloidal Dispersions: Suspensions, Emulssions, and Foams; Hohn Wiley & Sons: New York; 2002, pp505-515, where The above documents are hereby incorporated by reference;

i) determine the composition of the solvent mixture just sufficient to submerge the floating particles of the granular material;

j) Deviations from Einstein's equation to measure flow viscosity of hard spheres or other deviations from dispersive properties of hard spheres at higher concentrations.

In addition, interfacial potential values may be used alone or in combination with other interfacial potential values, for example, to specify the granular material itself, or to specify batches, batches, or shipments of granular material.

In order to achieve the purpose of the present invention, the product specification related to the interface potential performance value can be the value specifically measured by the above-mentioned interface potential performance test, or it can be created to reflect, express or notify a certain interface potential performance in the product specification Numerical or symbolic or other representations. It is also within the protection scope of the present invention to assign at least one performance value of the granular material related to the interface potential, or to derive a value from a component of the interface potential performance value. Thus, for example, interfacial potential-dependent properties such as wicking rates can be specified. Values derived from this property, such as work of adhesion, work of cohesion, or the difference between the two, can also be determined and specified. Since these values can be mathematically separated into components related to the strength of the interaction of the granular filler with itself and the probe fluid matrix, these separations can be used to specify the granular material. Combinations of each of these components are also possible. Thus, as noted above, "interfacial potential performance values" include both performance measures and derivatives or components of any such properties.

Another embodiment of the present invention is a product specification that includes at least one interfacial potential property value. The product specification may also include at least one morphological and/or chemical value. Product brochures can be part of a web page, product catalog, sales or purchase order, contract or waiver, etc. The present invention provides methods for conducting commercial activities using interfacial potential performance values in product specifications for batches, samples, batches and/or shipments. As noted above, this new method of doing business provides benefits to the industry. The present invention also provides a method of representing or identifying the grade, type and/or grade of granular material by at least one value of the interface potential, and conducting commerce using such a method. This also offers many benefits to the industry.

The invention will be more clearly illustrated by the following examples, which are merely exemplary in nature.

Example

Example 1

Standard grades of carbon black are available from a number of manufacturers. One Q/C specification for these standard grades is the DBP number. For dibutyl phthalate (DBP), the volume at maximum torque is a QA/QC measure of carbon black morphology.

DBP values were measured on six standard scales in a Brabender mixer with an apparatus for recording torque data. These data are reported in Table 2 below. Carbon blacks are ordered by their DBP number.

Determining the volume at maximum torque of another liquid is an example of a QA/QC test for the interfacial potential of carbon black and can be used to specify granular materials. For this example, water, a 60/40 glycol/water mixture (60 parts by volume ethylene glycol to 40 parts by volume water), ethylene glycol, and paraffin oil were used. Table 2 also shows the volume at maximum torque. These results show that the standard grade sequences are differently dependent on which liquid is used as the probe liquid. For example, looking at the data when using water, the interfacial potential value can increase or decrease as the DBP number increases. When these carbon blacks are used in fields where structure and interfacial potential are important factors, product properties may change unexpectedly accordingly. Therefore, to specify these granular materials, at least one interfacial potential property value should be included, especially on product specification sheets.

Table 2 sample name Volume at maximum torque for 5 fluids water 60% glycol 100% glycol DBP Paraffin oil ASTM Reference Carbon Black A6 205.5 152.6 128.3 128.7 130.65 ASTM Reference Carbon Black B6 238 142.3 119.5 121.7 123.75 ASTM Reference Carbon Black C6 154.55 94.6 74.9 80.4 83.05 ASTM Reference Carbon Black D6 122.2 81.5 69.8 74.05 75.9 ASTM Reference Carbon Black E6 130.8 103.3 88.9 95.25 98.1 ASTM Reference Carbon Black F6 227.3 156.2 133.9 137.9 139.6

Example 2

Manufacturers often produce the same product in different production plants. Regardless of where it is produced, the product must meet product specifications.

Table 3 shows data taken from the same grades of carbon black produced by four production plants. In this example, "% of maximum DBP" is the % of the largest DBP value in the table produced by factory E. The DBP number is measured as volume at maximum torque on a Brabender absorptometer with a device capable of recording torque data. Note: the DBP numbers are almost the same (within about 96% of the maximum value). The DBP value is part of today's product specification, and by this standard, all of these samples should be considered the same (ie, within specification).

The volume at maximum torque was also measured with three other liquids: ethylene glycol (EG), a 60/40 ethylene glycol/water mixture (60 parts by volume ethylene glycol to 40 parts by volume water), and pure water. This is an example of an interface potential performance test.

table 3 sample name Volume at maximum torque % of maximum DBP EG 60%EG water Factory A 97 77.1 108.8 17.15 Factory B 98.8 71.95 92.9 132.15 Factory C 97.8 72.8 90 138.35 Factory D 95.8 82.3 115.4 145.8 Factory E 100 73.5 91.9 100.35

As shown by the data in Table 3, the volumes obtained with other liquids were different for different plants. This shows that the interfacial potentials of these four samples are different, so the products are also different. Therefore, the product can be better specified if at least one of these interfacial potential values is included.

Example 3

The carbon black of Example 2 has a low DBP value. Similar tests were performed with carbon black grades of higher DBP specification. Samples were obtained from three production plants. The volume at maximum torque was also measured with DBP in a Brabender absorptometer with an apparatus for recording torque data and the results were expressed as % of maximum (plant F). The volume at maximum torque was also measured with ethylene glycol (EG), a 60/40 ethylene glycol/water mixture (60 parts by volume ethylene glycol to 40 parts by volume water) and pure water, and the results obtained are also shown in Table 4 .

Table 4 sample name Volume at maximum torque % of maximum DBP EG 60%EG water Factory F 100 115.3 150.5 217.1 Factory G 98.3 114.0 141.5 183.95 Factory H 97.2 111.5 138.9 208.2 Factory I 97.5 114.1 139.6 226.75

The data show that when measuring the value of the interface potential, the product grades produced by different factories are different. Therefore, including at least one interfacial potential value is useful for specifying these granular materials.

Example 4

Modern carbon black production plants can operate under various process conditions and are also able to produce QA/QC values (analytical properties) such as iodine value (I2 number), DBP number (DBPA), nitrogen surface area (N2SA), t-area (STSA) and almost the same product in shades. In Table 5 below, the upper rows show that the listed carbon blacks are all the same as measured by standard QA/QC values. However, when the Bartell method (described in Morrison, ID; Ross, S. Colloidal Dispersions: Suspensions, Emulssions, and Foams; Hohn Wiley & Sons: New York; 2002, pp210-212, incorporated herein by reference) through each A large difference can be seen when the interfacial potential is measured by the wicking rate of the two liquids up the packed powder bed. The unit of wicking rate is g ² /s.

table 5 Analysis performance 12 numbers 71 85.3 88 86.5 88.6 85.7 85.8 85.8 82.2 85.9 87.9 DBPA 108 106.9 108.2 106.5 108.1 104.9 104.4 105.9 104.5 102.9 107.8 N2SA 61.8 75.6 76 75.7 75.7 73.9 76.1 73.6 74.6 77 STSA 61.4 74.7 71.7 72.2 69.6 69.4 72.8 70.3 70.1 71.3 tone 89.3 105.5 99.2 98 99.3 104 98.1 94.1 98.3 102.9 94.8 Wicking rate water 0.0005 0.0011 0.0011 0.0007 0.0009 0.0006 0.0007 0.0006 0.0006 0.0009 0.0010 Formamide 0.0044 0.0062 0.0049 0.0039 0.0063 0.0049 0.0054 0.0029 0.0025 0.0045 0.0050 Ethylene glycol 0.0023 0.0011 0.0012 0.0008 0.0016 0.0011 0.0016 0.0007 0.0004 0.0012 0.0015 bromonaphthalene 0.0060 0.0023 0.0031 0.0017 0.0021 0.0017 0.0017 0.0017 0.0011 0.0020 0.0020 Pentane 0.0212 0.0046 0.0077 0.0029 0.0074 0.0091 0.0070 0.0038 0.0028 0.0049 0.0085 Tetrahydrofuran 0.0094 0.0055 0.0125 0.0047 0.0185 0.0065 0.0138 0.0062 0.0032 0.0090 0.0136

Thus, although these granular materials are all the same when measured on a standard scale, they differ in their interfacial potentials, and the method of the invention comprising assigning at least one interfacial potential performance value enables them to be distinguished.

Example 5

The previous examples used one interface potential parameter from each test. However, combinations of various parameters can also be used.

An absorptometer (commercially available from C.W. Brabender Instruments, Inc., 50 E. Wesley St., South Hackensack, NJ 07606) was used according to the procedure described in ASTM test D-2414-01. Dibutyl phthalate (DBP) was added to the carbon black sample located in the mixing chamber using a constant rate burette. The torque transducer detects the semi-plastic flow in which the viscosity increases from a free-flowing powder to a continuous substance. The absorptometer and burette are switched off when the torque has passed the maximum characteristic value in such a way that the maximum torque is achieved. The DBP volume per unit mass of carbon black was recorded as the DBP absorption number. CDBP values (ASTM D-3493) were obtained from a similar test using carbon black pre-pressed prior to testing.

The data are shown in Table 6, which also shows the iodine value and nitrogen and STSA surface area values. In Table 6, these morphological values are reported as % of maximum. NOTE: Based on all values shown, especially for standard liquid DBP, these materials can be considered the same.

Table 6 sample % of maximum DBP number at 70% (cc/100g) % of maximum CDBP at 70% (cc/100g) % of maximum iodine value (mg/g) % of maximum BET surface area (m ² /g) % of maximum STSA (m ² /g) CB-A 100 100 91.1 97.6 95.1 CB-B 99.2 96.4 95.6 95.1 92.7 CB-C 98.3 96.3 95.6 97.6 97.6 CB-D 99.2 94.0 97.8 100 100 CB-E 98.3 100 100 100 97.6

A similar absorption test procedure was then performed with paraffin oil, ethylene glycol, water, and a 60/40 mixture of ethylene glycol and water. The results are shown in Figure 1. As can be seen from Figure 1, the parameter values tested in ethylene glycol are different for each sample. The same goes for paraffin oil. When using a 60/40 glycol/water mixture (60 parts by volume of glycol to 40 parts by volume of water) or pure water alone, a clear separation of carbon black samples with the same morphology can be found. Additionally, the sequence of samples (carbon black samples shown in Figure 1 showing high and low values) varies with the solvent used. Thus, Figure 1 shows that carbon black samples considered identical by standard morphological tests were different from each other when tested with different liquids. Therefore, these specified carbon blacks can be used. Combinations of these values are also possible. Including morphological values can provide better product specification.

Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification of the invention and practice of the invention disclosed herein. The specification and examples of the invention are to be considered as exemplary only, with the true scope and spirit of the invention being indicated by the following claims and their equivalents.

Claims (67)

CLAIMS 1. A method of creating a product specification for a lot, batch or shipment of granular material comprising specifying at least one interfacial potential value for said batch, batch or shipment of granular material. 2. A method of conducting commercial activities with users, including the use of product specifications, including interface potential performance values, to request and/or provide a certain batch, batch or shipment of granular materials . 3. The method of claim 1, wherein the interfacial potential value is included on a product specification sheet, purchase order, invoice, contract, waiver, or combination thereof for a lot, lot, or shipment of granular material middle. 4. The method of claim 1, wherein said specifying includes determining at least one interface potential value for said lot, batch or shipment of granular material. 5. A method according to claim 4, wherein said determining comprises measuring or analyzing said batches, batches or shipments of granular material. 6. The method of claim 1, wherein said specifying includes characterizing the batch, lot or shipment of granular material with at least one value of the interface potential. 7. The method of claim 1, further comprising the step of specifying at least one morphological value for said lot, batch or shipment of granular material. 8. A method according to claim 7, wherein the morphological value is included on a product specification sheet for a lot, batch or shipment of granular material. 9. The method of claim 7, wherein the morphological value is surface area, particle size, structure, porosity, or a combination thereof. 10. The method of claim 1, further comprising the step of specifying at least one chemical value for said lot, batch or shipment of granular material. 11. A method according to claim 10, wherein the chemical value is included on a product specification sheet for a lot, batch or shipment of granular material. 12. The method according to claim 10, wherein the chemical values are pH, amount of functional groups and zeta potential. 13. The method of claim 1, wherein the particulate material is a carbonaceous material. 14. The method of claim 1, wherein the particulate material is carbon black. 15. The method of claim 1, wherein the particulate material is a metal oxide. 16. The method of claim 1 wherein the particulate material is fumed silica. 17. The method of claim 1, wherein the interfacial potential value is determined by absorptiometry. 18. The method according to claim 17, wherein the absorption measurement uses a liquid other than DBP or paraffin oil. 19. The method according to claim 18, wherein the absorption measurement uses water, glycol or a mixture thereof. 20. The method of claim 1, wherein the interfacial potential value is determined by the wicking rate method. 21. The method of claim 1, wherein the interfacial potential value is determined by the yield point method. 22. The method of claim 1, wherein the value of the interfacial potential property is determined by the interfacial potential vapor adsorption method. 23. The method of claim 1, wherein the interfacial potential value is determined by IGC. 24. The method of claim 7, wherein the morphological values are determined by liquid sorption, vapor sorption, microscopy or a combination thereof. 25. A method according to claim 7, wherein the morphological values are determined by adsorption using iodine, nitrogen, CTAB, DBP or paraffin oil. 26. A method of indicating or identifying a grade, brand or type of granular material comprising assigning at least one interfacial potential value to said grade, brand or type of granular material. 27. A method of doing business with customers comprising requesting and/or offering a certain grade, brand or type of granular material using interface potential performance values. 28. The method of claim 26, wherein said assigning includes determining at least one interfacial potential value for said grade, brand or type of particulate material. 29. The method of claim 28, wherein said determining includes measuring or analyzing said grade, brand or type of granular material. 30. The method of claim 26, wherein said assigning includes at least one interfacial potential value characterizing the grade, brand or type of particulate material. 31. The method of claim 26, further comprising the step of assigning at least one morphological value to said grade, brand or type of granular material. 32. The method of claim 31, wherein the morphological value is surface area, particle size, structure, porosity, or a combination thereof. 33. The method of claim 26, further comprising the step of specifying at least one chemical value for said grade, brand or type of granular material. 34. A method according to claim 33, wherein the chemical values are pH, amount of functional groups and zeta potential. 35. The method of claim 26, wherein the particulate material is a carbonaceous material. 36. The method of claim 26, wherein the particulate material is carbon black. 37. The method of claim 26, wherein the particulate material is a metal oxide. 38. The method of claim 26, wherein the particulate material is fumed silica. 39. The method of claim 26, wherein the interfacial potential value is determined using absorptiometry. 40. The method according to claim 39, wherein the absorption measurement uses a liquid other than DBP or paraffin oil. 41. The method of claim 39, wherein the absorptive measurement uses water, glycol, or a mixture thereof. 42. The method of claim 26, wherein the interfacial potential value is determined by the wicking rate method. 43. The method of claim 26, wherein the interfacial potential value is determined by the yield point method. 44. The method of claim 26, wherein the value of the interfacial potential property is determined by interfacial potential vapor adsorption. 45. The method of claim 26, wherein the interfacial potential value is determined by IGC. 47. The method of claim 31, wherein the morphological values are determined by liquid sorption, vapor sorption, microscopy, or a combination thereof. 48. The method of claim 31 wherein the morphological values are determined by adsorption using iodine, nitrogen, CTAB, DBP or paraffin oil. 49. A method for a granular manufacturer to provide granular material to a customer, comprising the step of specifying at least one interfacial potential value for the grade, brand or type of granular material. 50. A method according to claim 49, wherein said designation assists the manufacturer in providing the grade, brand or type of granular material to enable the user to achieve desired performance. 51. The method of claim 49, wherein said designation assists the user in obtaining the grade, brand or type of granular material to enable the user to achieve desired performance. 52. The method of claim 49, further comprising the step of assigning at least one morphological value to said grade, brand or type of granular material. 53. The method of claim 49, further comprising the step of assigning at least one chemical value to said brand or grade of granular material. 54. A method of ordering granular material comprising the step of ordering a grade, brand or type of granular material having at least one assigned interface potential performance value. 55. The method of claim 54, further comprising the step of specifying at least one interface potential value for a lot, lot or shipment of grade, brand or type of granular material. 56. A method according to claim 55, further comprising the step of specifying at least one morphological value for a lot, batch or shipment of grade, brand or type of granular material. 57. The method of claim 55, further comprising the step of specifying at least one chemical value for a batch, batch or shipment of grade, brand or type of granular material. 58. A method of improving identification of a grade, type or brand of granular material comprising the step of updating an existing product specification for a grade, type or brand of granular material by adding at least one interfacial potential value. 59. The method of claim 58, wherein said product instructions are in a catalog, website, brochure, granular material literature, advertisement, label, or a combination thereof. 60. A product specification for a grade, brand or type of granular material comprising at least one interfacial potential value. 61. The product brochure according to claim 60, wherein said product brochure is part of a web page. 62. A product specification according to claim 60, wherein said product specification is part of a product catalogue. 63. A product specification according to claim 60, wherein said product specification is part of a sales or purchase order. 64. The product specification according to claim 60, wherein said product specification is part of a contract or waiver of contract. 65. The product specification according to claim 60, further comprising adding morphological values, chemical values, or both morphological and chemical values to the product specification. 66. A method of distinguishing between two or more grades, brands or types of granular material comprising identifying an interface potential performance value for said grade, brand or type of granular material. 67. A method of identifying a grade, type or brand of granular material comprising the step of creating a product specification for the grade, type or brand of granular material including at least one interfacial potential value. 68. The method of claim 67, wherein said product specification appears in a brochure, catalog, website, contract, advertisement, or a combination thereof.