mixture of cement-supplementary cement material, method of making it and cement composition

专利摘要:
CEMENT-SCM MIXTURES WITH COMPACTED PARTICLES Cement-SCM mixtures employ particle compaction principles to increase the particle compaction density and reduce the interstitial spacing between cement and SCM particles. Particle compaction reduces the amount of water required to obtain a cement paste having a desired flow, decreases the water-cement ratio (w / cm), and increases initial and long-lasting strengths. This can be done by providing a fraction of hydraulic cement having a narrow PSD and at least a fraction of SCM having an average particle size that differs from the average particle size of the narrow PSD cement by a multiple of 3.0 or more, for produce a cement-SCM mixture having a particle compaction density of at least 57.0%.
公开号:BR112014009653B1
申请号:R112014009653-8
申请日:2012-10-17
公开日:2021-01-12
发明作者:John M. Guynn；Andrew S. Hansen
申请人:Roman Cement, Llc；
IPC主号:

专利说明:

[0001] [001] The invention is, in general, in the field of hydraulic and concrete cement. 2. RELEVANT TECHNOLOGY
[0002] [002] Supplementary Cement Materials ("SCMs"), such as ash dust, slag, natural pozzolans, and limestone, are often used to replace a portion of Portland cement in concrete. SCMs can produce an improved concrete with greater durability, less permeability to chloride, reduced creep, increased resistance to chemical attack, lower cost, and reduced environmental impact. The pozzolans react with the calcium hydroxide released during the hydration of the cement. Limestone can provide a reinforcing effect and nucleation sites.
[0003] [003] Portland cement, sometimes referred to as "cement clinker" or "OPC" (acronym for "common Portland cement"), is the most expensive component of concrete. The manufacture of cement clinker contributes an estimated 5-7% of all artificial CO2. There is a long-felt need, but not met, to reduce the consumption of cement clinker ("clinker"). There have been several academic conferences and publications dedicated to the concept of replacing a part of the clinker with SCM. Despite the overabundance of low-cost SCMs, the industry has failed to overcome the technical barriers to using SCMs more effectively. This failure, after years of research and discussion, to fully use readily available and less expensive SCMs to reduce clinker consumption, while doing so would reduce the cost and benefit the environment, means that conventional practices for using SCMs are inadequate. Hundreds of millions of tons of residual SCMs, such as ash dust and steel slag, continue to be discarded into the environment, worldwide, every year, at a cost to the producer and at an even higher cost. for the environment.
[0004] [004] SCMs are typically industrial wastes not intentionally produced to match OPC. Because OPC and SCMs are often produced for different reasons, by different industries, OPC manufacturers have little or no influence on the production of SCMs and SCM producers have little or no influence on OPC manufacturing. The result is that cement manufacturers continue to produce and optimize OPC for use alone, without considering how OPC behaves when replaced by SCMs.
[0005] [005] Cement manufacturers deliberately produce OPC having a wide particle size distribution ("PSD") (eg, between about 1-60 µm) in an attempt to strike a balance between conflicting effects and the demands for reactivity, resistance development rate, water demand, particle spacing, paste density, porosity, autogenous contraction, and milling cost. PSD and chemistry are selected to improve the use of OPC alone. SCM substitution is secondary and has little or no influence on how cement is manufactured. The slight increase in Blaine's fineness when clinker and SCM are intervened to compensate for the delay is the only commercial attempt to "optimize" cement for SCM replacement.
[0006] [006] SCMs are usually less reactive than clinker and delay the development of resistance by dilution. Although some OPCSMC mixtures may approach OPC resistance at later ages (> 56 days), initial resistance (1-28 days) can be severely impacted when more than about 10-20% of OPC is replaced by SCM. The initial loss of strength and / or the delayed setting times limit the use of SCM in concrete. The conventional solution is to "correct" the SCMs to make them more reactive, for example, by grinding them more finely, independently or by intermingling with the clinker. No solution solved the problems of underutilizing SCMs. In the meantime, residual SCMs continue to accumulate around the world in alarming quantities, and the separation between OPC production and the actual use of SCM persists. BRIEF SUMMARY OF THE MODALITIES DISCLOSED
[0007] [007] Hydraulic cements and SCMs are optimized for use with each other. In one aspect, cement-SCM mixtures can employ the principles of particle compaction to increase the particle compaction density ("PPD") and reduce the interstitial spacing between the particles. The production of cement and SCM fractions with compacted particles reduces the amount of water required to obtain a cement paste having a desired flow, decreasing the "water to total cement material ratio" (w / cm), and increases initial and long-lasting resistance. Mixtures of cement-SCM with compacted particles increase the density of the paste and decrease the demand for water, compared to OPC alone and conventional mixtures of cement-SCM, particularly intermodal materials having a greater Blaine than OPC.
[0008] [008] The high density of particle compaction can be achieved by optimizing the respective PSDs of the cement and SCM fractions, to reduce interstitial voids. Independently processing the cement and SCM fractions, while optimizing them to combine with each other, also allows the selection of PSDs and / or chemicals to optimize the individual contributions of each component and / or the overall synergy of the mixture.
[0009] [009] According to one embodiment, a fraction of hydraulic cement having a narrow PSD and at least a fraction of SCM having an average particle size, which differs from the average particle size of the narrow PSD cement by a multiple of 3, 0 or more, provide a cement-SCM mixture having a particle compaction density of at least 57.0%.
[0010] [010] These and other advantages and features of the invention will become more fully apparent from the description and the appended claims that follow, or can be learned by practicing the invention, as shown below. BRIEF DESCRIPTION OF THE DRAWINGS
[0011] [011] To further clarify the above mentioned advantages and characteristics and the other advantages and characteristics of the present invention, a more particular description of the invention will be presented with reference to its specific modalities, which are illustrated in the attached drawings. It is appreciated that these drawings represent only the illustrated modalities of the invention and are therefore not to be considered as limiting their scope. The invention will be described and explained with additional specificity and detail through the use of the accompanying drawings, in which:
[0012] [012] Figures 1A-1B are schematic flowcharts of illustrative methods of making hydraulic cement having a desired PSD and cement-SCM combinations;
[0013] [013] Figure 2 is a graph that schematically illustrates the sample PSDs of the cement and SCM components of a space-quality cement-SCM mixture;
[0014] [014] Figures 3A-3E are graphs that schematically illustrate the sample PSDs of the cement and SCM components of cement-SCM mixtures with compacted particles, illustrative;
[0015] [015] Figures 4A-4D schematically illustrate the grinding and grading systems of a single classifier, for example, to manufacture a narrow PSD hydraulic cement;
[0016] [016] Figures 5A-5D schematically illustrate the grinding and grading systems of two classifiers, for example, to manufacture a narrow PSD hydraulic cement;
[0017] [017] Figures 6A-6F schematically illustrate the grinding and grading systems of three classifiers, for example, to manufacture a narrow PSD hydraulic cement; and
[0018] [018] Figures 7A-7F schematically represent the grinding and grading systems of four classifiers, for example, to manufacture a narrow PSD hydraulic cement. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS I. INTRODUCTION
[0019] [019] Cement-SCM mixtures include fractions of cement and SCM that are optimized for a high particle compaction density ("PPD") of cement paste (eg, within mortar or concrete) during the early stages, when good flow characteristics are desired. High PPD mixtures optimize the properties of the cement fraction that provide strength, improve the space filling capacity of the SCM fraction (s) and, in many cases, obtain additional long-term strength of at least part of the SCM fraction (s).
[0020] [020] The concept of "particle compaction", using well classified aggregates to increase aggregate compaction density, has been used to great advantage in concrete to reduce the amount of cement paste required to produce concrete having a desired strength. By way of illustration, a single mixture of concrete aggregate sand may include sand with a natural PPD of 55%. In this way, the amount of sand mass includes 45% useless voids between the particles. As a result, the sand mixture contains at least 45% by volume of cement paste. In this hypothesis, simply using a second aggregate of different average particle size, such as fine-gravel or rock, can increase the particle compaction density of the aggregate fraction from 55% to 70-85%, which substantially decreases the amount of cement paste required to produce concrete of the same strength. The addition of a third aggregate can further increase the compaction density of the aggregate and reduce the volume of the cement paste. The use of well classified aggregates, selected to optimize the aggregate compaction density, can be used to design high strength concrete with an optimized cement paste volume.
[0021] [021] Similar particle compaction concepts have not been used in OPC or cement-SCM mixtures, where a wide particle size distribution (eg, Fuller distribution) or a narrower distribution (eg ., as advocated by Tsivillis) continues to be used. In practical terms, the only way to produce OPC with high PPD using conventional methods is to flatten the PSD curve and extend the end points (eg, decrease the d10 and / or increase the d90). However, simply lowering the d10 below what has been found to be optimal increases grinding costs, without a corresponding benefit. For example, cement particles below a certain size (eg 0.5-1.5 µm) dissolve almost immediately when mixed with water. Increasing the amount of cement particles that rapidly dissolve in water does not increase the PPD of the remaining cement particles. On the other hand, increasing the d90 of the cement particles may, in fact, increase the PPD of the cement particles in the cement paste. However, the net effect can be to reduce the overall surface area and the reactivity of the cement, which reduces the rate of resistance development and increases the number of large cement particles that cannot fully hydrate, but remain an expensive filling.
[0022] [022] In view of the foregoing limitations, a typical practice is to grind Type I, II and V cements in order to have a d10 of about 1-2 µm and a d90 of about 35-45 µm. Florida Rock reported that cement grinding can be optimized to reduce grinding cost and increase cement strength, providing an OPC in which 70% by volume of cement particles have particle sizes that exceed the range of 2-32 µm. In general, narrowing (or increasing the slope) of the OPC PSD curve provides certain known benefits and detriments. The grinding costs can be reduced and the reactivity of the cement can increase, but also the demand for water and the depletion of the cement paste can increase. For example, grinding costs are reduced, but depletion increases when less fine cement is produced. The reactivity increases when there are fewer coarse particles, but the reduced PPD of the narrower PSD cements increases the water demand. Because of known problems associated with narrow PSD cements, vertical cylinder mills and high pressure grinding cylinders, which are naturally capable of producing cements with a narrower PSD than ball mills, have been deliberately modified to extend the PSD of the cement (eg, by increasing the number of times the cement particles are released into the grinding bed, before they are finally removed as a finished product by the classifier).
[0023] [023] In summary, and in view of longstanding experience and practice, the OPC PSD is deliberately maintained, by essentially all cement manufacturers, within the specified limits of d10 and d90, with little or no deviation to achieve a desired balance between conflicting effects and demands for reactivity, rate of resistance development, water demand, particle spacing, paste density, porosity, autogenous contraction, and milling cost. This practice makes perfect sense when considering how OPC behaves alone. It is irrational in the context of using SCM because it fails to consider how the deficiencies of narrow PSD cements can be mitigated, or used advantageously, by combining such cements with SCM particles of complementary size. Thus, the thinking that motivates "optimization" by industry practice is the main obstacle that prevents OPC from being optimized for use with SCMs. Such thinking has prevented cement specialists from even trying to produce cements with highly compacted particles - there has been no purpose or technical route to achieve such a result.
[0024] [024] As a result, the OPC's PPD is rarely, if ever, measured, much less reported. However, recent work by Zhang et al. (discussed below) identified commercial OPCs with particle compaction densities of less than about 50% (i.e., the OPC mass amount is more than 50% void). Thus, the volume of water required to initially fill the voids between the cement particles and displace the air during the initial mixing is greater than the volume of the cement itself. Even before explaining that any additional "mixing water" is required to wet the aggregates and provide sufficient excess water in the cement paste, to provide the desired spreading of the mortar and / or the collapse of the concrete, the first water that should be Added to the OPC is essentially "waste" water, which does not contribute to the flowability of the paste and concrete. It is "excess" water after such "space filling" (or interstitial) water that contributes most to providing the desired flow.
[0025] [025] The high void space between the cement particles in the OPC can be explained by analogy with the high void space between the sand particles in an individual mix of sand aggregate (except that the OPC particle compaction density can still be worst). It would be wasteful to produce concrete with only sand as the aggregate, instead of sand and rock, because this can more than double the amount of cement required to produce the concrete with the same strength. This also produces concrete that is more likely to contract and develop cracks, initially and over time.
[0026] [026] Similarly, the use of OPCs that have a PPD of 50% or less is "wasteful". Such waste is not because "space filling" water is expensive (water is less expensive than cement, except when considering the cost of water-reducing adjuvants). It is because space filling water adversely reduces the strength of the cement paste, unnecessarily increasing the "water to cement ratio" (w / c) of the cement paste, compared to a hypothetical cement that has a higher PPD and a smaller volume of empty spaces that must be filled with space filling water. By way of illustration, a hypothetical cement with a PPD of 75% would include half the empty space of a cement with a PPD of 50%. This would cut in half the amount of "space filling" water required to move the air and fill the interstitial voids during the initial mixing. The other half of the "space filling" water, otherwise required for wetting the OPC, would then be released as "mixing water" (or "convenience water"), available to provide the desired flow of the cement paste. and concrete. The result would be a substantial reduction in the total water required to produce the cement paste and concrete having the desired flow. This, in turn, would substantially reduce w / cm and increase resistance for a given flow. Because the effect of w / cm on resistance is not linear, a given percentage of reduction in w / cm typically increases resistance by a substantially greater amount. And because aw / cm is responsible for both fractions of higher reactive hydraulic cement and less reactive SCM, it is possible that changes in w / cm may have a more dramatic effect on strength (exaggerating the decrease in w / cm). cm net).
[0027] [027] In contrast to conventional cements, cements designed as disclosed in this document use particle compaction principles similar to those used in compacting concrete aggregates, to increase the PPD of solid particles in the cement paste. The projected cements contain fractions of cement and SCM with complementary particle sizes that increase the overall PPD compared to each fraction alone. The cement and SCM fractions can be optimized in particle size to provide their respective greatest benefit to the overall mix. The chemistry of the cement and SCM fractions can also be optimized to further increase SCM replenishment and / or provide other desired properties.
[0028] [028] According to one modality, a projected cement is obtained with compacted particles "replacing" at least some of the ultrafine cement particles that dissolve in the OPC with SCM particles that do not dissolve (or that dissolve more slowly), ultrafine, which fill the fine pore spaces with solid particles. The ultra-fine SCM particles displace water and / or dissolved cement minerals that would otherwise be required to fill the pore spaces between the larger cement particles, when preparing the new cement paste having a desired flow. At least some of the coarse cement particles can be "replaced" by coarse SCM particles, of similar size, or even of a larger size, which can reduce or eliminate unhydrated cement cores in the hardened concrete. Coarse SCM particles are generally less expensive than coarse cement particles and can be classified more coarsely to further increase PPD and reduce the amount of water and / or dissolved cement minerals that would otherwise be required to fill the spaces between the particles, when the new cement paste is created having a desired flow. For example, engineered cements can include ultra-thick SCM particles, classified to increase their particle compaction effect in relation to the fraction of finer aggregate in concrete or mortar. In this mode, the entire cement-SCM aggregate system can be more adequately compacted into the particles, compared to conventional concrete and mortar. II. PARTICLE SIZE, PARTICLE COMPACT DENSITY, HYDRATION, WATER DEMAND, AND DEVELOPMENT OF RESISTANCE A. BASIC PRINCIPLES
[0029] [029] Water is both a reagent for hydration and causes cement materials to flow and consolidate. As long as a cement material has enough water, so that it can be placed and shaped as desired and become properly consolidated, it will typically also have enough water to make cement binders hydrate and develop strength. This is true for hydraulic cements and similar pozzolans. All things being equal, decreasing w / cm improves both initial and later resistance.
[0030] [030] For the particle compaction principles of SCM cement mixtures to be effective, it is advantageous to consider both the short and long term dynamics of the cement and SCM particles and to select the cement and SCM fractions appropriately. It is not enough to select particles that provide a high degree of initial particle compaction (i.e., when water is first added). Consideration should also be given to how particles behave over time, eg, during some or all of the following illustrative stages: 1) mixing with water to form new concrete or other cement material, 2) storage and / or transport before use, 3) disposition, consolidation, molding, and / or surface finishing, 4) initial and / or final grip, and 5) development of initial and / or long-lasting strength.
[0031] [031] Cement particles are much more reactive than SCM particles and change size faster than SCM particles as a function of time, both in the early stages, before the setting, and in the later stages, after the handle. Short-term changes in particle size (eg, dissolution contraction) after mixing with water, during storage and / or shipping, and during disposal, consolidation and / or finishing can dramatically affect PPD, rheology, and flow characteristics of cement paste. After catching, however, the rheological effects of changing particle size and PPD become much less relevant, if not irrelevant.
[0032] [032] Hydraulic cements, such as Portland cement, are generally more reactive than SCMs and can beneficially provide the high initial resistance, heat and excess lime required for pozzolanic reactions. For this reason, hydraulic cement particles dissolve more quickly than SCMs and, in general, suffer a greater reduction in particle size, compared to SCM particles, especially in the early stages, before catching, when flow is most affected. It is advantageous to explain the effects of short-term dissolution on the size of the hydraulic cement and SCM particles, when planning a cement-SCM mixture to have a desired PPD. It may also be advantageous to explain the proportion to which cement and SCM particles become hydrated or react over time (eg, between 1-28 days), to determine how both cement and SCM particles affect the development of resistance during this time. Cement particles that never fully hydrate, but include unreacted cement cores, do not give their potential to give full strength and contain "wasted cement".
[0033] [033] The particles of hydraulic cement and SCM, in general, react completely. Because the pozzolanic reaction is not apparent until after the initial setting (ie, for at least about 3-7 days), and because the limestone and other charges are essentially inert, the particle size of most SCMs can be assumed have a constant particle size during the initial stages, before the initial catch. However, the particle size of the hydraulic cement fraction is dynamic. The present disclosure explains the dynamic changes in the particle size of the hydraulic cement fraction and its effects on rheology.
[0034] [034] The rate of dissolution of hydraulic cement particles can depend on several factors, including the chemistry and inherent reactivity, the amount of water available, the particle's morphology, and the competition reactions. A discussion of how Portland cement hydrates, including the depth of reaction as a function of time, is presented in Osbaeck et al., "Particle Size Distribution and Rate of Strength Developement of Portland Cement", J. Am. Ceram. Soc., 72 [2] 197-201 (1989). Table 1 by Osbaeck et al. provides the following estimates of the reaction depth as a function of time:
[0035] [035] The preceding table is for cement paste that includes 100% OPC in unspecified w / c, without any SCM. The depth of the reaction as a function of time is likely to be different when the variables are changed. It should be emphasized that Osbaeck et al. do not disclose how to manufacture engineered cement-SCM mixtures. Neither Osbaeck et al disclose how to design narrow PSD cements to prepare projected cements or for any purpose. The assumptions and principles used in this document, when designing narrow PSD cements, had been developed for the purpose of designing cements designed with compacted particles that contained fractions of hydraulic cement and SCM. However, once you understand how to design cements designed with compacted particles, as disclosed here, to improve flow in the early stages and increase the potential of hydraulic cement to provide short and long-lasting strength, the preceding table can provide insights into how you could select a Portland cement having a narrow PSD to match one or more fractions of SCM.
[0036] [036] For example, in a mixture where it is desired for some of the Portland cement particles to fully hydrate in 1 day, and others to fully hydrate in 3 days, 7 days, 28 days, and 91 days, respectively, and assuming that the cement particles are perfectly spherical (in which case the reaction depth is equal to the radius, and hydration occurs uniformly around the perimeter of the particle), a hypothetical distribution of perfectly spherical cement particles could include the following fractions of size particle, where the "ideal" diameter is twice the radius, or the depth of the reaction from all sides):
[0037] [037] Thus, for the various particle size fractions within a cement particle distribution to be fully hydrated in 1, 3, 7, 28 and 91 days, an ideal example Portland cement with spherical cement particles could have a PSD extending over a range of about 0.8-14 µm. Grinding cement particles down to less than 0.8 µm could be wasteful if they increase water demand, without providing a corresponding strength benefit. Providing cement particles above 14 µm could be wasteful, as they do not fully hydrate, but include "wasted" cores as an expensive charge.
[0038] [038] However, the range of particle sizes in the preceding example is for particles that are perfectly spherical. Because the cement particles are irregular and can have aspect ratios (length to width) between about 1-2, cement particles larger than 0.8-1.2 µm can be essential and fully hydrated in 1 day, cement particles larger than 1.6 - 2.4 µm can be essential and fully hydrated in 3 days, etc. However, the larger cement particles can behave more like spherical particles, since hydration occurs for days or weeks and the irregularity becomes less pronounced. Smaller cement particles may be more sensitive to spherical spacing because, when their rough edges are rounded, they can be completely dissolved. In addition, particles with fractures, sharp edges and porosity tend to hydrate faster and are more susceptible to rapid dissolution.
[0039] [039] In another example, where the smaller cement particles have an aspect ratio of 2, a particle of 1.6-2.4 µm in length and 0.8-1.2 µm in width could be essentially and totally hydrated after one day. Consequently, the "diameter" of a particle with a length of 1.6-2.4 µm and an aspect ratio of 1.5-2 can "effectively" be about 2 µm. Thus, the lower endpoint of the PSD of the non-uniform cement particles can be about 2 µm, instead of 0.8 µm. The grinding of non-uniform cement particles smaller than 2 µm can be unnecessary and wasteful. In addition, for larger cement particles with an aspect ratio of about 1.5 and / or that hydrate more quickly than perfect spheres as a result of irregular morphology, the upper end point of the PSD of such cement particles it can be about 21 µm, instead of 14 µm. Thus, the present invention includes narrow PSD cements with particles ranging from about 2-21 µm (e.g., they have a d1 of 2 µm and a d99 of 21 µm). Depending on the shape of the PSD curve, the d10 of this hypothetical narrow PSD cement could be about 1-3 µm greater than 2 µm and the d90 could be about 2-6 µm less than 21 µm. Other variables can affect the rate of dissolution of cement particles, including, but not limited to, the type (s) and / or quantity (s) of SCM in a cement-SCM mixture, chemical and cement reactivity, quantity of water available in the system over time, room temperature, water evaporation rate, heat of hydration, internal heat build-up, or plate thickness.
[0040] [040] It must be kept in mind that the depths of the reactions observed in Osbaek were observed in the OPC having a d10 of perhaps 1.5 µm and a d90 of perhaps 45 µm. When the effects of the Le Chatelier principle are considered, the rate of dissolution and hydration of the smallest cement particles can affect the rate and depth of hydration of the larger cement particles, at both early and later ages. After the smaller cement particles have dissolved and saturated the water with the dissolved ions (eg, calcium, magnesium, silicate, aluminate, and aluminum-ferrite ions), the additional hydration of the cement particles only occurs as the solid hydration products precipitate, releasing water molecules to further dissolve the cement particles. The rate of such additional hydration is related to the rate of formation of hydration products, bearing in mind that water is a reagent and is used, to some extent as hydration products are formed. However, for each water molecule consumed during the formation of a precipitated hydration product, several are released to continue the ion dissolution process, followed by the formation of precipitated hydration products. In the end, all the water is used in the formation of hydration products, it is captured as interstitial water and / or it is evaporated, during which time the hydration essentially stops.
[0041] [041] The inventors postulate that reducing the proportion of ultrafine cement particles, which dissolve immediately and / or before the initial setting, increases the dissolution rate of the larger cement particles, according to Le Chatelier's principle. If the cement fraction includes fewer ultrafine cement particles that preferentially compete for water, more water will remain available to dissolve the larger cement particles, according to Le Chatelier's principle. If saturation, not particle size or surface area per se, is assumed to be the main limiting rate variable for dissolution, and if some or all of the cement particles, which would otherwise dissolve immediately or before initial handle, are removed and replaced with SCM that does not dissolve or slowly dissolves, the larger cement particles will dissolve and hydrate faster. In such a case, Osbaek's hydration depth graph can attenuate the reaction depth rate of a narrow PSD cement having a higher d10 in a cement-SCM mixture. It is postulated that increasing the reaction rate of all cement particles causes the smaller particles that remain to dissolve more quickly, compared to if they had to compete with even smaller cement particles for water, if such particles had not been removed (eg, as with the OPC).
[0042] [042] It is further postulated that removing the smallest cement particles (eg, below 2 µm) will cause the next largest fraction of cement particles (eg, 2-4 µm) to become more completely hydrated on the first day. Removing cement particles below about 2 µm "matches the playing field" and allows particles up to about 4 µm to become fully hydrated in 1 day, according to Le Chatelier's principle. Achieving an equal, or better, dissolution of the larger particles compared to the cement with the smaller particles avoids the "wasted energy" of grinding the smaller cement particles.
[0043] [043] This exercise can be repeated until the smallest cement particle on the narrow end of the PSD cement is identified, which is essential and fully hydrated in 1 day (ie, because it is able to "see" a effective "ocean of water", in which it dissolves, free of competition from smaller particles). As long as a sufficient surface area is available for hydration, it may be beneficial to further narrow the PSD of the cement fraction, raising the lower particle size tip range, with an increased reaction rate of the remaining larger cement particles. For example, eliminate cement particles below about 5-8 µm and replace them with slow-dissolving SCM or that does not "dissolve" the resulting smaller cement particles (ie, 8-12 µm) to hydrate more quickly, according to the Le Chatelier principle. Obviously, to the extent that all remaining cement particles react faster, according to the Le Chatelier principle, and are able to result in the desired setting time and the development of initial strength, it may be unnecessary to include any particles of cement that completely hydrate and / or dissolve within 1 day. The removal of some or all of the coarse particles that do not become fully hydrated after 28, 56 or even 91 days is expected to provide additional benefit, by increasing the reactive surface area of the remaining cement particles. The dissolution rate can be further increased by modifying the cement chemistry (eg, increasing the mineral content of tricalcium).
[0044] [044] By narrowing the PSD, the cement particles, as a whole, can contribute sufficient calcium ions, for the water to become fully saturated with calcium ions immediately or shortly after mixing, even in the absence of particles that immediately dissolve or dissolve before the initial handle, the final handle, or even 1 day. Achieving a desired dissolution rate while raising the d10 of the cement can also provide sufficient hydration heat for the desired setting time and temperature and pH high enough to initiate the pozzolanic reaction, thereby benefiting the strength gain from the fraction of SCM. Increasing the PPD of a cement-SCM mixture decreases w / cm, which would be expected to further benefit the setting time and the short and long term resistances. The inclusion of finely ground limestone can additionally trigger the dissolution of calcium ions from the cement particles, according to the Le Chatelier principle (eg, providing nucleation sites that accelerate the formation of hydration products and the removal of dissolved ions from the aqueous system, which speeds up the dissolution of the remaining cement particles).
[0045] [045] The d10 of an example narrow PSD cement, useful for compacting the particle with an SCM, can range from about 2-15 µm, 3.5-12.5 µm, 5-11.5 µm, or 7-10 µm. To the extent that it is desired for all cement particles to be fully hydrated in 91 days, 56 days, or 28 days, and depending on d10 and other factors that affect the depth of the reaction as a function of time, as discussed above , the d90 of an example narrow PSD cement, useful for compacting the particles with one or more SCMs, can be between about 10-35 µm, about 12-30 µm, about 14-27 µm, or about 16-24 µm.
[0046] [046] In summary, including ultrafine cement particles (eg, below about 2-5 µm) can be wasteful and undesirable because they require excessive energy to grind, react excessively fast, and delay hydration of short and / or long duration of the larger cement particles. They can create a very viscous, non-particulate gel and yield in a more unsatisfactorily compacted particle system. Replacing the ultrafine cement particles with SCM particles that dissolve slowly or do not dissolve provides a better compacted system with a larger volume of particulate solids and a smaller volume of interstitial water. Including coarse cement particles is wasteful as they do not fully hydrate, but leave unhydrated cores that act as an expensive load, both in terms of manufacturing cost and in terms of the environmental affected area (eg, CO2 " wasted "and the energy used to manufacture unhydrated cement load cores). In this way, providing a narrow PSD cement with a larger d10 and a smaller d90, compared to OPC, and combining the cement with the complementary SCM particles, of a certain size, maximizes the beneficial effects of conferring strength of the cement fraction. , at the same time less water demand ew / cm and increasing resistance.
[0047] [047] Because a narrow PSD cement has less PPD compared to OPC (eg, having a Fuller distribution), it is necessary according to the disclosure to increase the PPD of the global projected cement-SCM mixture by selecting a or more SCMs that provide complementary particles, of a certain size. According to one embodiment, at least a fraction of SCM is provided that has an average particle size (MPS) that differs from the MPS of the narrow PSD cement fraction by a multiple of at least 3.0 more preferably at least about 3.25, 3.5, 3.75, 4, 4.25, 4.5, 5, 5.5 or 6, to produce a cement-SCM mixture having an "initial PPD" (before adding water ) of at least 57.0%, more preferably at least about 58%, 60%, 62.5%, 65%, 70%, or 75%.
[0048] [048] For example, if the d50 of a narrow PSD cement is 15 µm, an illustrative cement-SCM mixture with compacted particles may include a first fraction of thinner SCM having a d50 of 5.0 µm or less and a second fraction of SCM having a d50 of 45 m or greater, to obtain a PPD of 57.0% or greater. However, it may be permissible, in some cases, for the difference between the MPS of a fraction of SCM and the MPS of the narrow cement fraction of PSD to be less than a multiple of 3.0, provided that the MPS of the other fraction of SCM differ from the MPS of the narrow PSD cement fraction by a multiple of 3.5 or greater and / or provided that the PPD of the cement-SCM mixture is at least 57.0%.
[0049] [049] In some cases, it may be desirable to have little or no overlap between the PSDs of the cement and SCM fractions or even an interval between the upper particle size of a fraction and the lower particle size of the next larger fraction. For example, the amount of overlap can be less than about 25%, preferably less than about 18%, more preferably less than about 12%, even more preferably less than about 8%, and more preferably still less than about 4% by weight of the combined fractions. In some cases, there may be an interval of at least about 2.5%, based on the particle size between d10, d5 or d1 of a fraction and d90, d95 or d99 of the next smaller fraction, more preferably at least about of 5%, 7.5%, 10%, 12.5%, 15%, 17.5% or 20% (eg, a "negative overlap" or "overlap" of less than about -2 , 5, -5%, -7.5%, -10%, -12.5%, -15%, -17.5% or -20%).
[0050] [050] The use of separate thin and thick SCM fractions on one or both sides of the narrow PSD cement fraction is beneficial for many reasons, including, but not limited to, reduced capillary pore volume, which reduces permeability and transport and increases durability and resistance to chemical attack, reduced autogenous contraction and creep, a reduced amount of water within the cement paste to produce a given flow, and increased volumetric paste density (ie, when normalized for specific gravities of the fractions of SCM and cement). B. EVOLUTION OF ROMANO® CEMENT
[0051] [051] Projected compacted particle cements are an improvement over OPC, which in general has a PPD of less than 50% and includes a substantial amount of coarse cement particles that never fully hydrate and produce "wasted" cement cores. OPC is, in general, only optimized for use with itself and regardless of its behavior when used with SCMs. This is especially true when OPC is used by concrete manufacturers to prepare "on-site mixtures" with SCMs or when SCMs and OPC are otherwise "self-mixed" by the end user.
[0052] [052] Cements with compacted particles, projected, disclosed in this document, are also an improvement over the intermittent cement-SCM mixtures, which seek to "correct" the SCMs and make them more reactive by intimate grinding with the OPC. Intermittent cement-SCM mixtures are generally more reactive and produce greater resistance than mixtures on site or other self-combining cement compositions. However, intermittent mixtures often have a higher water demand as a result of increased fineness, may have an even lower PPD than OPC, and may require larger (and / or more expensive) amounts of water reducers.
[0053] [053] Engineered compacted particle cements are also an improvement over the inventors' previous work in U.S. Patent Nos. 7,799,128 and 7,972,432 ("first generation patents"). First generation patents, incorporated by reference, describe "first generation" Roman Cement®, in which most or all of the coarse cement particles normally found in the OPC are "removed" (eg, for have a d85, d90 or d95 of 20 µm or less) and "replaced" by coarse pozzolan particles. Ash dust or other pozzolans can have powders extracted to remove fine particles and reduce PSD overlap between the cement and pozzolan fractions to reduce water demand. First generation Roman Cement® increases the liquid reactivity of the cement (eg, the net amount of strength conferred by a given weight or volume of cement) by eliminating or reducing unhydrated cement cores and using less coarse ash dust expensive or other pozzolan particles, rather than more expensive cement particles.
[0054] [054] The National Institute of Standards and Technology ("National Institute of Standards and Technology") (NIST) tested several "first generation" ash cement-dust mixtures and identified potential commercially viable mixtures, in which 20-35% of cement were replaced by an equivalent volume of ash dust and that essentially matched, or exceeded, OPC resistance in all stages between 1-192 days and that had acceptable setting times. However, water demand was an issue for some mixtures tested by NIST due to technical limitations of the grading and grinding equipment used to provide the test materials. As a result, some mixtures tested by NIST required significant but economically viable amounts of high-variety water reducer to maintain the same flow as 100% OPC. Despite the high fineness of the cement fractions, the thicker ash dust mitigated the demand for water and autogenous contraction.
[0055] [055] The "second generation" Roman Cement® was developed to deal with water demand and / or increase the reactivity of SCM. In the second generation Roman Cement®, a narrow PSD cement is combined with one or more fractions of SCM to form binary, ternary, and quaternary mixes of "space quality". Replacing at least a part of the ultrafine cement particles with SCM particles that dissolve more slowly decreases the water demand, freeing up the water to lubricate the larger particles. It also increases the liquid reactivity of the SCM whenever the finer SCM particle is more reactive than the thicker SCM particles.
[0056] [056] A ternary cement-SCM mixture is disclosed in US Provisional Application No. 61 / 324,741, filed on April 15, 2010. The PSD cements narrow, the binary, ternary, and quaternary combinations made with them, and the methods for making narrow PSD cements and mixtures are more particularly described in US Provisional Application No. 61 / 365,064, filed on July 16, 2010, in US Provisional Application No. 61 / 413,966, filed on November 15, 2010 , in US Provisional Application No. 61 / 450,596, filed on March 8, 2011, in International Patent Application No. PCT / US11 / 32442, filed on April 14, 2011 (WO 2011130482, published on October 20, 2011 ), and in US Patent Application No. 13 / 183,205, filed on July 14, 2011 (collectively "second generation patents", incorporated by reference).
[0057] [057] The first and second generation cement-SCM mixes can be designed to have a global PSD that is similar to that of the OPC (eg, a Fuller distribution). They are also "space-quality" because the average particle size (MPS) of the thickest SCM fraction is substantially larger than the MPS of the thinner cement fraction. In the case of ternary mixtures, the MPS of the cement fraction can also be substantially greater than the MPS of the fine SCM fraction. This is in contrast to on-site mixes and other self-combining mixes of OPC and SCM, as well as intermodified SCM cement mixes, which are not of space quality, but have substantial or total overlap between the PSDs of the cement and SCM fractions.
[0058] [058] The other examples of space quality cement-SCM mixtures are described in Zhang, et al., "A new gap-graded particle size distribution and resulting consequences on properties of blended cement," Cement & Concrete Composites 33 ( 2011) 543-550 ("Zhang I"), incorporated by reference. In a hypothetical Fuller distribution of space quality, schematically illustrated in Table 1 (page 544), the average particle size (MPS) of the second fraction of the medium (16 µm) is 2.67 times larger than the MPS of the third thinnest fraction (6 µm), and the MPS of the third thickest fraction (45 µm) is 2.81 times greater than the MPS of the second middle fraction (16 µm). The cement-SCM mixtures tested had space quality fractions similar to the corresponding cement clinker fractions shown in Table 3 (pages 544-545), where the MPS of the clinker fraction (15.08 µm) is 2, 89 times greater than the MPS of the finer SCM fraction (5.21 µm), and the MPS of the thicker SCM fraction (44.21 µm) is 2.93 times greater than the MPS of the clinker fraction ( 15.08 µm). As seen in Figs. 2 (a) and 3 (a) by Zhang I, there is a significant overlap between the PSDs of the three space quality cement clinker fractions. As shown in Table 4 (p. 546), Zhang I space-quality cement-SCM mixtures were prepared using various combinations of cement clinker, blast furnace slag, ash dust, steel slag, and limestone . The "reference cement" was prepared by grinding together 36% of blast furnace slag, 25% of cement clinker, and 39% of ash dust. Space-quality cement-SCM mixtures had PPDs (or "maximum solids volume concentration (%)") ranging from 50.17 - 53.63, greater than Portland cement PPDs (46.88) and reference cement (44.73).
[0059] [059] The other examples of SCM-cement mixtures are described in Zhang, et al., "Study on optimization of hydration process of blended cement," J. Therm. Anal. Calorim DOI 10.1007 / s10973-011-1531-8 (April 8, 2011) ("Zhang II"), incorporated by reference. Zhang II's cement-SCM mixtures include five fractions, any of which can be characterized as first fine SCM, second fine SCM, third middle cement, fourth thick SCM, and fifth thickest SCM. According to Table 4 by Zhang II, three SCM-cement mixtures were prepared using various combinations of cement clinker, blast furnace slag, ash dust, and steel slag, and the "reference cement" was prepared grinding together 36% of ground granulated blast furnace slag (GGBFS), 25% of cement clinker, and 39% of ash dust. The cement-SCM mixtures had PPDs (or "maximum solids volume concentration (%)") ranging from 55.62 - 56.62, which were higher than the PPDs of Portland cement (49.12) and Cement reference (45.40). The Zhang I and II cement-SCM mixtures are similar to, and can be examples of, the second generation Roman Cement®.
[0060] [060] Zhang I and II also provide the following equation, useful for determining the particle compaction density of a cement material: ρwet - ρw φ = −−−−−−− (1) ρc - ρw where φ = maximum volume concentration of solids in a cement paste ρwet = maximum wet paste density ρw = water density ρc = cement density
[0061] [061] Although used to determine the compacting densities of OPC, cement-SCM mixtures, and the reference cement disclosed in Zhang I and II, the preceding equation can be used to determine the compacting densities of cement particles with compacted particles, designed, within the scope of the invention, characterized as "third generation" Roman Cement®. For the purposes of this disclosure, the "maximum wet paste density" can be understood as the density of a cement paste that includes only enough water to wet the cement and SCM particles and fill the empty spaces between the particles in the paste. cement (eg without significant water run-off from the cement paste). III. SCM-CEMENT MIXTURES WITH COMPACTED PARTICLES A. EXAMPLE MATERIALS AND DEFINITIONS 1. HYDRAULIC CEMENT
[0062] [062] The terms "hydraulic cement" and "cement" shall include Portland cement, cements defined by ASTM C150 (Types IV) and similar materials containing one or more of the four clinker minerals: C3S (tricalcium silicate), C2S (dicalcium silicate), C3A (tricalcium aluminate), and C4AF (tetracalcium aluminum ferrite). Other examples of hydraulic cement include white cement, calcium aluminate cement, cement with a high alumina content, magnesium silicate cement, magnesium oxychloride cement, oil well cements (eg ., Types VI, VII and VIII), magnesite cements, and their combinations. Ground granulated blast furnace slag (GGBFS) and other slags that include one or more clinker minerals can also function as hydraulic cement. They are also classified as SCMs. Some highly reactive Class C ash dust has high-cementation properties and can be classified as "hydraulic cement".
[0063] [063] In line with defining the GGBFS, slag and reactive ash dust as "hydraulic cement", alkali-activated cements, sometimes known as "geopolymer cements", are also examples of "hydraulic cements". It will be appreciated that when geopolymer cements or other highly reactive pozzolans are used, two or more separately graded pozzolan fractions can be combined together to increase the particle compaction density of the global particle system to at least 57.0, alone or in combination with the less reactive or non-reactive SCM load. 2. SUPPLEMENTARY CEMENT MATERIALS
[0064] [064] The terms "Supplementary Cement Material" and "SCM" will include materials commonly used in industry as partial replacements for Portland cement in concrete, mortar and other cement materials, or in combined cements or by self-combining on the user Final. Examples range from highly reactive materials (eg, GGBFS), moderately reactive materials (eg, Class C ash dust, steel slag, silica fume, activated metakaolin, metastable forms of CaCO3), less active substances (eg, dust from Class F ash, volcanic ash, natural pozzolans, traces, and metastable forms of CaCO3), and essentially non-reactive materials and fillers (eg, ground limestone, ground quartz, precipitated CaCO3 , Precipitated MgCO3). Through alkali activation, it is possible that some SCMs also become hydraulically active. In a way, the pozzolanic reaction is a form of activation by alkali, albeit by more weakly basic calcium ions compared to strongly basic sodium or potassium ions, as in typical geopolymer cements. B. Particle Sizes in Cement-SCM Mixtures with Compacted Particles 1. Narrow PSD Hydraulic Cements
[0065] [065] Cement-SCM mixtures with compacted particles having improved strength and / or reduced water demand include a narrow PSD cement fraction. According to one modality, the PSD of the cement fraction can be defined by its d10, d50 and d90, with the d10 approaching the lower end point ("LEP") of the PSD, the d90 approaching the upper end point ("UEP") of the PSD, and the d50 approaching the average particle size ("MPS") of the PSD. In other modalities, d1, d5, d15, or an intermediate value can be used as the close LEP, d85, d95, d99, or an intermediate value like the close UEP, and d40, d45, the d55, the d60 or an intermediate value like the nearby MPS.
[0066] [066] Narrow PSD cements are typically characterized as having a margin (eg, UEP - LEP) and a ratio of end points (eg, UEP / LEP) that are less than the margin and the ratio of OPC end points, respectively, with substantially less frequency. The decrease in UEP reduces the volume of unhydrated cement cores, which increases hydration efficiency. The increase in LEP reduces the demand for water. In one embodiment, a narrow PSD cement fraction may have an LED that is substantially larger, and an UEP that is substantially smaller, than the respective OPC LEP and UEP (eg, for both Fuller distributions and Tsivillis).
[0067] [067] For example, in comparison with OPC of Types I, II, IV and V, as defined by ASTM C150, the d10 of a narrow PSD cement can be substantially greater than the d10, and in most cases, the d90 of a narrow PSD cement may be substantially less than the d90 of these types of OPC. In comparison to the Type III OPC, as defined by ASTM C150, the d10 of a narrow PSD cement can be substantially greater than the d10, and the d90 of the narrow PSD cement can be equal to or less than the d90, Type III OPC.
[0068] [068] In one embodiment, the PSD of the cement fraction can be defined by the upper and lower "end points" of the PSD UEP and LEP (eg, d90 and d10). PSD can also be defined by the margin or difference between UPE and LPE (eg, "d90 - d10"). In another modality, the PSD of the cement fraction can be defined by the ratio of the upper and lower end points UEP / LEP (eg, d90 / d10). In yet another modality, PSD can be defined by the lower median range LEP and MPS (eg, d10 and d50). In yet another modality, PSD can be defined by the lower median ratio MPS / LEP (eg, d50 / d10). In another modality, the PSD can be defined by the upper median range MPS and UEP (eg, d50 and d90). In yet another modality, PSD can be defined by the median ratio higher than UEP / MPS (eg, d90 / d50). PSD can also be defined by any combination of the preceding and / or similar methodologies to increase reactivity and / or decrease water demand, compared to OPC and conventional cement-SCM mixtures.
[0069] [069] To ensure that the cement fraction has a PSD within the desired parameters, care must be taken to accurately determine the particle size. The particle size of perfectly spherical particles can be measured by diameter. Although ash dust is generally spherical due to how it is formed, Portland cement and some SCMs can be non-spherical (i.e., when ground from larger particles). For these, the "particle size" can be determined according to accepted methods for determining the particle sizes of ground or otherwise non-spherical materials. The particle size can be measured by any acceptable method and / or by methods yet to be developed. Examples include sieving, optical or electron microscope analysis, laser diffraction, x-ray diffraction, sedimentation, elutriation, microscope counting, the Coulter counter, and Dynamic Light Scattering. The. PSD DEFINITION BY LOWER AND HIGHER FINAL POINTS
[0070] [070] The upper end point (UEP) can be selected to provide the desired reactivity and / or fineness in combination with, or independent of, the lower end point (LEP), and / or a desired particle compaction density at combination with one or more thicker SCMs. The UEP (eg, d85, d90, d95 or d99) can be equal to or less than about 35 µm, 30 µm, 27.5 µm, 25 µm, 22.5 µm, 20 µm, 18 µm , 16.5 µm, 15 µm, 13.5 µm, 12 µm, 11 µm, or 10 µm. The limit of the lower UEP range can be about 8 µm, 9 µm, 10 µm, 11 µm, 12 µm, 13 µm, 14 µm or 15 µm.
[0071] [071] The lower end point (LEP) can be selected to provide the desired water demand and / or fineness in combination with, or independent of, the upper end point (UEP), and / or a particle compaction density in combination with one or more thinner SCMs. LEP (eg, d1, d5, d10 or d15) can be equal to or greater than about 1.0 µm, 1.25 µm, 1.5 µm, 1.75 µm, 2 µm, 2 , 5 µm, 3 µm, 4 µm, 5 µm, 6 µm, 7 µm, or 8 µm. The upper LEP limit can be about 6 µm, 8 µm, 10 µm, 12 µm or 15 µm.
[0072] [072] UEP and LEP can also define the margin (UPE - LEP) of hydraulic cement. For example, depending on the UEP and LEP of the cement and the capacity or limitations of the processing equipment to produce narrow PSD cements, the margin may be less than about 30 µm, 25 µm, 22.5 µm, 20 µm, 17.5 µm, 15 µm, 13 µm, 11.5 µm, 10 µm, 9 µm, 8 µm, 7 µm, 6 µm, 5 µm, or 4 µm. B. PSD DEFINITION BY UEP / LEP
[0073] [073] In another embodiment, the UEP / LEP ratio can define a narrow PSD cement having the desired reactivity, fineness and / or particle compaction density in combination with one or more SCMs. The UEP / LEP (eg, d90 / d10) of narrow PSD cements may be less than the ratio of Type IV cements as defined by ASTM C-150. According to different modalities, the UEP / LEP can be less than, or equal to, about 25, 22.5, 20, 17.5 15, 12.5, 10, 8, 6, 5, 4.5 , 4, 3.5, 3, 2.5 or 2.
[0074] [074] It will be appreciated that the PSD definition of a narrow PSD cement for the UEP / LPE ratio is not limited by a particular UEP or LEP or particle size range. For example, a first hypothetical narrow PSD cement having a d90 of 15 µm and a d10 of 3 µm has a UEP / LEP (i.e., d90 / d10) of 5 and a margin (d90 - d10) of 12 µm. By comparison, a second hypothetical narrow PSD cement having a d90 of 28 µm and a d10 of 7 µm has a UEP / LEP (i.e., d90 / d10) of 4 and a margin (d90 - d10) of 21 µm. Although the margin of the second hypothetical narrow PSD cement is greater, the UEP / LEP (i.e., d90 / d10) is smaller than that of the first hypothetical narrow PSD cement. In this way, the second hypothetical cement has a narrower PSD compared to the first hypothetical cement, as defined by UEP / LEP (i.e., d90 / d10), although the margin is greater. ç. DEFINITION OF PSD BY LOWER MEDIUM BAND LEP A MPS
[0075] [075] In another modality, the Lower Middle Range LEP to MPS can define a narrow PSD cement having a desired reactivity, fineness and / or a desired particle compaction density in combination with one or more SCMs. In general, the reactivity and fineness (e.g., Blaine) of a hydraulic cement increases as MPS decreases and water demand and fineness decrease as LEP increases, all things being equal.
[0076] [076] The upper end point MPS of the lower median range can be selected to provide the desired reactivity, fineness and / or particle compaction density in combination with, or independent of, any of the LEP or UEP. The MPS (d40, d45, d55, d60) can be less than, or equal to, about 25 µm, 22.5 µm, 20 µm, 18 µm, 16 µm, 15 µm, 14 µm, 13 µm, 12 µm, 11 µm, 10 µm, 9 µm, 8 µm, 7 µm, 6.5 µm, 6 µm, 5.5 µm, or 5 µm, with a lower range limit of 3 µm, 3.5 µm, 4 µm, 4.5 µm, 5 µm, 6 µm, 7 µm, 8 µm, 10 µm or 12 µm.
[0077] [077] The lower LEP end point of the lower median range can be selected to provide the desired water demand, fineness and / or particle compaction density in combination with, or independent of, any of the MPS or UEP. According to several modalities, the LPE (eg, d1, d5, d10 or d15) can be equal to, or greater than, about 1.0 µm, 1.25 µm, 1.5 µm, 1 , 75 µm, 2.0 µm, 2.5 µm, 3 µm, 4 µm, 5 µm, 6 µm, 7 µm, or 8 µm. The upper LEP range limit can be about 5 µm, 6 µm, 7 μm, 8 μm, 10 μm, 12 μm or 15 μm. d. PSD DEFINITION BY LOWER MEDIAN REASON MPS / LEP
[0078] [078] In another embodiment, the ratio of MPS / LEP lower average particle sizes (eg, d50 / d10) can define a narrow PSD cement having a desired reactivity, fineness and / or density of the particle compaction in combination with one or more SCMs. The MPS / LEP ratio of PSD cements narrow within the disclosure will generally be less than the MPS / LEP ratio of Type I-V cement as defined by ASTM C-150. According to several modalities, the d50 / d10 ratio can be less than or equal to 7.5, 6.5, 5.5, 5, 4.5, 4.25, 4, 3.75, 3.5 , 3.25, 3, 2.75, 2.5, 2.25, 2, 1.75 or 1.5. and. PSD DEFINITION BY THE TOP MEDIUM BAND MPS TO UEP
[0079] [079] In another modality, the upper median range MPS to UEP can define a narrow PSD cement having a desired reactivity, fineness and / or particle compaction density in combination with one or more SCMs. In general, the reactivity and fineness (e.g., Blaine) of hydraulic cement increases as MPS decreases, and water demand and fineness decrease as UEP increases, all things being equal.
[0080] [080] The lower end point MPS of the upper median range can be selected to provide a desired reactivity, water demand, fineness and / or particle compaction density in combination with, or independent of, any of the UEP or LEP. According to several modalities, the MPS (d40, d45, d55, d60) can be less than, or equal to, about 25 µm, 22.5 µm, 20 µm, 18 µm, 16 µm, 15 µm, 14 µm, 13 µm, 12 µm, 11 µm, 10 µm, 9 µm, 8 µm, 7 µm, 6.5 µm, 6 µm, 5.5 µm, or 5 µm and / or greater than, or equal to, about 3 µm, 3.25 µm, 3.5 µm, 4 µm, 4.5 µm, 5 µm, 5.75 µm, 6.5 μm, 8 μm, 10 μm or 12 μm.
[0081] [081] The upper end point (UEP) of the upper median range can be selected to provide the desired reactivity, water demand, fineness and / or particle compaction density in combination with, or independent of, any of the LEP or the MPS. According to several modalities, the LPE (eg, d1, d5, d10 or d15) can be equal to, or greater than, about 1.0 µm, 1.25 µm, 1.5 µm, 1 , 75 µm, 2 µm, 2.5 µm, 3 µm, 4 µm, 5 µm, 6 µm, 7 µm, or 8 µm. The upper UEP limit can be less than, or equal to, about 35 µm, 30 µm, 27.5 µm, 25 µm, 22.5 µm, 20 µm, 18 µm, 16.5 µm, 15 µm, 13.5 µm, 12 µm, 11 µm, or 10 µm. The limit of the lower UEP range can be about 8 µm, 9 µm, 10 µm, 11 µm, 12 µm, 13 µm, 14 µm or 15 µm. f. PSD DEFINITION BY UPPER MEDIUM REASON UEP / MPS
[0082] [082] According to another modality, the ratio of the average particle sizes greater than UEP / MPS (eg, d90 / d50) can define a narrow PSD cement having a reactivity, fineness and / or compacting density of the particle in combination with one or more SCMs. According to various embodiments of the invention, the d90 / d50 ratio can be in the range of about 1.25 to 6, about 1.5 to 5.5, about 1.75 to about 5, about 2 , 0 to 4.5, about 2.25 to 4.25, about 2.5 to 4.0, about 2.75 to 3.75, about 2.9 to 3.6, or about 3.0 to 3.5. 2. ILLUSTRATIVE SCM FRACTIONS
[0083] [083] The PSD of one or more fractions of the SCM can be defined by the d10, d50 and d90, with the d10 approaching the lower end point (LEP) of the PSD, the d90 approaching the upper end point ( UEP) of the PSD, and the d50 approaching the average particle size ("MPS"). In other modalities, d1, d5, d15 or an intermediate value can be used for the nearby LEP, d85, d95, d99 or an intermediate value for the nearby UEP, and the d40, d45, d55 , the d60 or an intermediate value for the nearby MPS. In some cases, the PSD of a fraction of a fine SCM can be defined mainly or exclusively in terms of the MPS and / or the UEP, while the PSD of a fraction of a thick SCM can be defined mainly or exclusively in terms of the MPS and / or LEP. The. FRAIN SCM FINE
[0084] [084] Mixing a fraction of fine SCM with a narrow PSD cement can "replace" at least part of the ultrafine cement particles, assist in dispersing the cement particles, filling the fine pore spaces, increasing fluidity, increase resistance, and decrease permeability.
[0085] [085] To obtain particle compaction relative to narrow PSD cement, the MPS of the narrow PSD cement fraction can be at least about 3.0 times, 3.25 times, 3.5 times, 3.75 times, 4 times, 4.5 times, 5 times, 5.5 times, or 6 times the MPS of the fine SCM fraction (eg, about 3.0-10 times, 3.25-8 times or 3.5-6 times). In some cases, the projected cement-SCM mixture may include one or more fractions of coarse SCM which, together with the narrow PSD cement fraction, provide sufficient particle compaction density that the fine SCM fraction can be merely of grade of space relative to the cement fraction (eg, where the MPS of the cement fraction is less than 3.0 times, 2.8 times, 2.7 times, 2.6 times, or 2.5 times the MPS of the fine SCM fraction).
[0086] [086] The UEP of the fine SCM fraction can be selected to be less than, approximately equal to, or greater than, the LEP of the narrow PSD cement fraction. In general, the lower the UEP of the fine SCM fraction in relation to the LEP of the cement fraction, the greater the compaction density of the particle. According to various embodiments of the invention, the degree of overlap can be less than about 25%, 18%, 12%, 8%, 4% or 2% by weight of the combined fractions. In other modalities, there may be a gap of at least about 1%, 2.5%, 5%, 7.5%, 10%, 12.5%, 15%, 17.5% or 20% between the UEP of thin SCM and the UEP of PSD cement narrow.
[0087] [087] The UEP (eg, d85, d90, d95 or d99) of a thin SCM can be less than about 18 µm, 15 µm, 12 µm, 10 µm, 9 µm, 8 µm, 7 µm , 6 µm, 5 µm, 4.5 µm, 4 µm, 3.5 µm, or 3 µm. The lower limit of the UEP range can be about 1 μm, 2 μm or 3 μm. LEP (eg, d1, d5, d10 or d15) can be equal to, or greater than, about 0.01 µm, 0.05 µm, 0.1 µm, 0.5 µm, 1, 0 µm, 1.25 µm, 1.5 µm, 1.75 µm, 2 µm, 2.5 µm, 3 µm, 4 µm, or 5 µm. The upper limit of the LEP range can be about 8 µm, 6 µm, 5 µm or 4 µm. B. SCM GROSSO FRACTION
[0088] [088] Mixing a fraction of coarse SCM with a narrow PSD cement can "replace" coarse cement particles, greatly increase particle compaction, provide a filling effect using a less expensive component, decrease aw / cm, increase fluidity, increase resistance, reduce contraction, and reduce creep.
[0089] [089] To obtain particle compaction in relation to narrow PSD cement, the MPS of the thick SCM fraction can be at least 3.0 times, 3.25 times, 3.5 times, 3.75 times, 4 times , 4.5 times, 5 times, 5.5 times, or 6 times the MPS of the narrow PSD cement fraction (e.g., about 3.0-10 times, 3.25-8 times, or 3, 5-6 times). In some cases, the projected cement-SCM mixture may include a fraction of thin SCM and / or a second fraction of thicker SCM which, together with the narrow PSD fraction, provides sufficient particle compaction density than the SCM fraction coarse may be merely of degree of space in relation to the cement fraction (eg, where the MPS of the coarse SCM fraction is less than 3.0 times, 2.8 times, 2.7 times, 2.6 times, or 2.5 times the MPS of the narrow PSD cement fraction).
[0090] [090] The LEP of the thick SCM fraction can be selected to be less than, approximately equal to, or greater than, the UEP of the narrow PSD cement fraction. In general, the higher the LEP of the coarse SCM fraction in relation to the UEP of the cement fraction, the greater the compaction density of the particle. According to various embodiments of the invention, the degree of overlap can be less than about 25%, 18%, 12%, 8%, 4% or 2% by weight of the combined fractions. In other modalities, there may be a gap of at least about 1%, 2.5%, 5%, 7.5%, 10%, 12.5%, 15%, 17.5% or 20% between LEP of the thick SCM and the PSD cement LEP narrow.
[0091] [091] The LEP (eg, d5, d10 or d15) of a thick SCM can be equal to, or greater than, about 8 µm, 10 µm, 12.5 µm, 15 µm, 17.5 µm, 20 µm , 22.5 µm, 25 µm, 30 µm, 35 µm, 40 µm, or 50 µm, with an upper limit of the LEP range of about 30 µm, 40 µm, 50 µm, 60 µm, 70 µm, 80 µm or 90 µm. The UEP (e.g., d85, d90, d95 or d99) of a thick SCM can be less than about 300 µm, 250 µm, 200 µm, 175 µm, 150 µm, 125 µm, 110 µm, 100 µm , 90 µm, 85 µm, 80 µm, 75 µm, 70 µm, 65 µm, or 60 µm, with a lower limit of the UEP range of about 30 µm, 40 µm, 50 µm, or 60 µm. ç. SECOND THICK SCM
[0092] [092] In the case where the cement-SCM mixture includes a narrow PSD cement fraction having a relatively low UEP and / or a thick SCM fraction having a relatively low UEP, it may be desirable to include a second thick SCM fraction which has an MPS greater than the MPS of the first fraction of the thick SCM, advantageously it is a LEP greater than the UEP of the first thick SCM (eg, to provide additional particle compaction in relation to the narrow PSD cement fraction and / or fine aggregate in concrete or mortar).
[0093] [093] The MPS of the second fraction of thick SCM may differ by a multiple of 3.0 or more from the MPS of the first fraction of thick SCM (e.g., to provide a fraction of ultra thick SCM) and / or fine aggregate (eg, sand) to maximize the particle's compaction potential. Alternatively, the second fraction of coarse SCM may be merely of degree of space in relation to the first fraction of coarse SCM and / or the fine aggregate (eg, where the MPS of the second fraction of coarse SCM differs by a multiple of less than 3.0, 2.75, 2.5, 2.0, or 1.5 in relation to the MPS of the first fraction of coarse SCM and / or fine aggregate). C. EXAMPLE MANUFACTURING METHODS
[0094] [094] Figure 1A is a flow chart illustrating an example method 100 for manufacturing hydraulic cement having a narrow PSD. Example manufacturing devices are illustrated in Figures 4A-4D, 5A-4D, 6A-6F and 7A-7E (discussed below). In action 102, the cement clinker (eg, the clinker used to prepare Type I-V Portland cement or Type VI-VII oil well cement) is ground to an initial fineness and / or PSD. This can be done by a known or modified grinding device, such as a rod mill, vertical cylinder mill ("VRM"), high pressure grinding cylinder, hammer mill, or ball mill. The desired fineness and / or PSD of the initial cement can be selected based on subsequent grading and grinding processes again. The d10 of the initial ground cement will advantageously be as high or higher than the d10 of the narrow PSD cement.
[0095] [095] In action 104, the initial ground cement is processed using one or more separators, to produce the cement fractions having different PSDs, including at least a finer fraction, which can be collected without further modification, and at least a fraction thicker. The finer cement fraction has a d90 that can equal, approach, or be within, a specified deviation from the d90 of the final cement product. The finer cement fraction will typically have a lower d10 than the initial crushed cement by removing the coarse particles. The coarse fraction can optionally have the powders extracted one or more times to further remove the fine particles and produce a coarse cement, best suited for subsequent grinding, without forming an excessive amount of ultrafine cement particles. The fines produced by extracting the powders can be mixed with the finer fraction.
[0096] [096] In action 106, the coarse fraction (s) produced by classification 104 is (are) ground using an appropriate grinding device, such as a stick mill, a VRM , a fine grinding cylinder press, a high pressure grinding cylinder, a ball mill, an impact ball mill, a hammer mill, a jet mill, a dry ball mill, a grinding mill ultrasonic, or another mill designed to grind the cement particles and produce one or more cement fractions again ground to a desired d90, preferably without producing an undesired amount of ultrafine particles. A re-ground cement intermediate can be processed one or more times by the optional grading action 108, to produce one or more additional fine cement fractions having a desired d90 and d10 and a thicker cement fraction that can be re-ground. The grinding again 106 and the optional classification 108 can be carried out by the same or different device used for the initial grinding 102.
[0097] [097] In action 110, one or more classified fine fractions are mixed with one or more coarse fractions ground again, to produce one or more cement products having a desired d90 and d10. The mixing can be carried out by an established dry mixing apparatus and / or one or more classifiers described above and / or illustrated in the Figures.
[0098] [098] In one embodiment, it may be desirable to remove one or more fine fractions and / or the final material to increase d10, as desired. The fine particles removed typically have a high value and can be advantageously used in applications where high-fineness cements are desired, such as in preparing plaster. The removed fines can alternatively be used as a combination material for OPC or other cements, to increase Blaine's fineness.
[0099] [099] Figure 1B is a flow chart illustrating an example method 150 for the manufacture of cement-SCM mixtures with compacted particles. In step 152, a narrow PSD cement is obtained. In step 154, one or more SCMs are obtained. In step 156, one or more SCMs are ground and / or graded to produce fine and coarse SCM fractions (eg, using any apparatus described in this document for grinding and separating cement). In step 158, the narrow PSD cement is combined with the thin and coarse SCM fractions to produce a cement-SCM mixture having a particle compaction density of at least 57.0%. The preceding method can be adapted to produce a binary cement-SCM mixture (eg, fine cement fractions and coarse SCM), a ternary mixture (eg, fine SCM fractions, narrow PSD cement, and Coarse SCM), or quaternary mixture (eg, thin SCM, narrow PSD cement, fraction of first coarse SCM, and fractions of second coarse SCM). D. SCM-CEMENT MIXTURES WITH EXAMPLE COMPACTED PARTICLES
[0100] [0100] Cement-SCM mixtures with compacted particles in general have a high PPD to reduce water demand, or the amount of water required to achieve a desired flow, which decreases aw / cm and increases resistance compared to similarly proportioned cement-SCM mixtures that do not have well-compacted particles (eg, mixtures on site, intermittent mixtures, and mixtures of space quality, where none of the fractions has an MPS that differs from the MPS by a fraction adjacent by at least 3.0 and / or having a PPD greater than 57.0). According to one embodiment, a narrow PSD cement is combined with one or more fractions of SCM to produce an SCM cement having an initial PPD (eg, after mixing with water and before the initial setting, or within 15 minutes, 30 minutes, 60 minutes, 120 minutes, or 180 minutes of mixing with water) of at least 57.0%, or at least about 58%, 59%, 60%, 62.5%, 65%, 67 , 5%, 70%, or 75%. Cement-SCM mixtures with illustrative compacted particles include binary, ternary and quaternary mixtures of cement and SCM.
[0101] [0101] Figures 2 and 3A-3E show the PSDs of the cement and SCM fraction of several cement-SCM mixtures. Figure 2 is a graph that schematically illustrates, for comparison purposes, the PSDs of the fine SCM, cement, and thick SCM fractions of a space-quality cement-SCM mixture, for example, having a PPD of less than 57.0 (ie, between 50.17-53.63). Figures 3A-3E are graphs that schematically illustrate cement-SCM mixtures with compacted particles, for example. A characteristic of the space quality mix of Figure 2 is the considerable overlap in the PSDs of the three adjacent fractions, and even some overlap between the thin and thick SCM fractions. Another feature is a lesser separation between the MPS of all three fractions (i.e., an MPS multiple of less than 3.0 times between adjacent fractions). The result is a PPD that is only marginally greater than the PPD of a corresponding OPC (i.e., 46.88).
[0102] [0102] In contrast, the PSDs of cement-SCM mixtures with compacted particles, for example, illustrated in Figures 3A-3E, have little or no overlap and / or have greater separations between the MPS of each adjacent fraction. Figure 3A schematically illustrates an example ternary mixture, in which there is minimal overlap between the fine and cement SCM fractions and the cement and coarse SCM fractions, and no overlap between the thin and coarse SCM fractions. In addition, the MPS multiple between adjacent fractions is 3.0 times or greater. Figure 3B schematically illustrates another example ternary mixture, in which there is virtually no overlap between adjacent fractions and the MPS multiple between adjacent fractions is 3.0 times or greater. Figure 3C schematically illustrates another example ternary mixture, in which there is no overlap between adjacent fractions and even a space between the smallest particles of the thick SCM and the largest particles of cement. The MPS multiple between adjacent fractions is even greater.
[0103] [0103] Figure 3D schematically illustrates an example quaternary mixture, in which there is no overlap between adjacent fractions and a space between the first and the second fraction of thick SCM. The MPS multiple between adjacent fractions is 3.0 or greater. Figure 3E schematically illustrates another example quaternary mixture, in which there are spaces between all adjacent fractions and the MPS multiple between adjacent fractions is even greater.
[0104] [0104] In one embodiment, a binary cement-SCM mixture with compacted particles includes a narrow PSD cement, as described in this document, and a single fraction of SCM having an average particle size (MPS) (eg, d50) which differs from the MPS (eg, d50) of the narrow PSD cement fraction by a multiple of at least 3.0, 3.25, 3.5, 3.75, 4, 4.25, 4 , 5, 5, 5.5 or 6 (e.g., a multiple ranging from 3.0-10, 3.25-8 or 3.5-6). In one embodiment, the single SCM fraction comprises a thick SCM fraction with at least 3.0 times, 3.25 times, 3.5 times, 3.75 times, 4 times, 4.25 times, 4, 5 times, 5 times, 5.5 times or 6 times the MPS of PSD cement narrows. In another embodiment, the single SCM fraction comprises a thin SCM, so that the narrow PSD MPS cement is at least 3.0 times, 3.25 times, 3.5 times, 3.75 times, 4 times , 4.25 times, 4.5 times, 5 times, 5.5 times or 6 times the MPS of the single SCM fraction. In some modalities, there may be no overlap in the PSDs of the cement and SCM fractions. Some overlap may be allowed, as long as the MPSs of the cement and SCM fractions are sufficiently different, so that the overall mixture has a high PPD (eg, at least 57.0%). Binary cement-SCM mixtures with compacted particles may be suitable for use alone or may require or benefit from combining with one or more additional SCMs to form a ternary or quaternary mixture.
[0105] [0105] In another modality, a ternary cement-SCM mixture includes narrow PSD cement and the first and second SCM fraction. The first SCM fraction can be a thick SCM having an MPS (eg, d50) that is at least 3.0 times, 3.25 times, 3.5 times, 3.75 times, 4 times, 4, 25 times, 4.5 times, 5 times, 5.5 times, or 6 times (eg, ranging from 3.0-10, 3.25-8 or 3.5-6 times) the MPS (p .d., d50) of PSD cement narrow. The second fraction of SCM can be a thin SCM, so that the narrow PSD MPS of the PSD is at least 3.0 times, 3.25 times, 3.5 times, 3.75 times, 4 times, 4, 25 times, 4.5 times, 5 times, 5.5 times or 6 times the MPS of the second SCM fraction. In one embodiment, only one of the SCM fractions is "compacted particles" in relation to the cement fraction (ie, the MPSs differ by a multiple of at least 3.0), while the other SCM fraction is merely "quality" of space "(ie, MPSs differ by a multiple of less than 3.0). This is permissible as long as the mixture has a high PPD (i.e., at least 57.0).
[0106] [0106] In yet another embodiment, a quaternary cement-SCM mixture can include a third SCM fraction that differs from the first and second SCM fraction. The third SCM fraction can simply be a different type of SCM with a similar or overlapping PSD, such as the thick SCM fraction, and / or it can provide a fourth PSD that additionally increases the particle compaction of the overall mix. For example, the first and second fraction of SCM can comprise one or more types of pozzolan (eg, ash dust, natural pozzolan, or slag), and the third fraction of SCM can comprise a non-pozzolanic material (p eg ground limestone or siliceous mineral). Alternatively, one or both the first and the second SCM fraction may comprise non-pozzolanic material (s) and the third SCM fraction may comprise the pozzolan. In one embodiment, the MPS of the third SCM fraction (eg, ultra-thick SCM fraction) can be at least 3.0 times the MPS of the thick SCM fraction. In yet another embodiment, the MPS of the third SCM fraction can be less than 3.0 times the MPS of the thick SCM fraction. E. EXAMPLE MANUFACTURING SYSTEMS
[0107] [0107] Figures 4A through 7F illustrate examples of fabrication systems for making a narrow PSD cement and / or one or more fractions of SCM having a desired PSD. A grinding apparatus and classifiers known in the art or modified can be used to produce narrow PSD cement and SCM cement particles with compacted particles, eg ball mills, high pressure grinding cylinders, vertical cylinders, rod mills, jet mills, hammer mills, high efficiency classifiers, screens, and the like. Illustrative grinding and separation equipment is available from one or more FLSmidth, Polysius or Pfeiffer. In general, the use of more classifiers allows more pronounced particle size cuts and facilitates the production of more accurate PSDs for the cement and / or SCM fractions. If a reference number is not explicitly described, it will be understood to be the same as a similar reference number that is described in a different figure.
[0108] [0108] Figure 4A illustrates a manufacturing system 400 for processing material 402 and includes the first mill 404 to produce the first milled material 406, which is sent to separator 408 to produce fine fraction 410 and coarse fraction 412 , which is ground again in the second mill 414. The ground material 416 again is combined with the fine fraction 410 to produce the product 418.
[0109] [0109] Figure 4B illustrates a manufacturing system 420 for processing material 422 and includes the first mill 424 to produce the first milled material 426, which is sent to separator 428 to produce product 430 and the thick fraction 432, which is ground again in the second mill 434. The ground material 436 is introduced into separator 428 and contributes to the final product 430.
[0110] [0110] Figure 4C illustrates a fabrication system 440 for processing material 442 which includes the first mill 424 to produce milled material 446, which is sent to separator 448. The thick material 452 is recycled back to the first mill 444 to form a coarse grinding circuit. The fine material 450 is ground again in the second mill 454 to produce the product 456.
[0111] [0111] Figure 4D illustrates a fabrication system 460 for processing material 462 which includes a single mill 464, which produces milled material 466, and a single separator 468, which produces product stream 470 and a coarse fraction 472, which is returned to the 464 mill.
[0112] [0112] Figure 5A illustrates a manufacturing system 500 for processing material 502 which includes a coarse grinding circuit consisting of coarse mill 504, which produces ground material 506, and the first separator 508a, which produces the first fraction coarse 512a, which is returned to the coarse mill 504 to grind again, and a first fine fraction 510, which is fed to the second separator 508b. The second separator 508b produces the fine fraction 515 and the thick fraction 512b, which is fed to the fine mill 514 to produce the refilled material 516, which is combined with the fine fraction 515 to produce the product 518.
[0113] [0113] Figure 5B illustrates a manufacturing system 520 that differs from system 500 in that it includes separate coarse and fine grinding circuits to process material 522. The coarse grinding circuit includes coarse mill 524, which produces the first milled material 526, the first separator 528a, which produces the finer fraction 530 and the thicker fraction 532a, which is recycled back to the coarse mill 524. The fines grinding circuit includes the fines mill 534, which produces the re-ground material 536, the second classifier 528b, which produces the product 538, and the second coarse fraction 532b, which is recycled back to the fines mill 534.
[0114] [0114] Figure 5C illustrates system 540, which differs from system 520 of Figure 5B in that the second separator 548b is used to classify folded the initial milled material 546 and the first fine material of the mixture 550 and the fine material ground again 556 to produce product 558.
[0115] [0115] Figure 5D illustrates system 560, which differs from systems 500, 520 and 540 in that it only includes a single grinding device 564, but two separation devices 568a and 568b (since they can be integrated inside a vertical cylinder with the initial separator around a perimeter of the grinding table and a single integrated high efficiency classifier). The coarse fractions 572a, 572b are ground again by the mill 564.
[0116] [0116] Figure 6A illustrates a manufacturing system 600 for processing material 602 which includes a coarse grinding circuit consisting of coarse mill 604 and first separator 608a, which produces the first coarse fraction 612a, recycled back to the coarse mill 604 for grinding again, and the first fine fraction 610a, fed to the second separator 608b. The second separator 608b produces the second fine fraction 610b and the second thick fraction 612b, which is fed to the third classifier 608c, part of a fines grinding circuit that includes the fines mill 614. The re-milled material 616 of the fines 614 is fed to the third separator 608c, which produces the third fine fraction 610c, which is combined with the second fine fraction 610b to produce the product 618, and the third thick fraction 612c, which is recycled back into the fines mill 614. Figure 6B illustrates system 620 which differs from system 600 in that the second coarse fraction 632b is fed to the fines mill 634, instead of the third classifier 628a.
[0117] [0117] Figures 6C-6E illustrate manufacturing systems 640, 660, 680, which differ from systems 600, 620 in that the product is produced by mixing the products of the coarse and fine grinding circuits in a single classifier. Figure 6F illustrates the manufacturing system 600 'for processing material 602', which includes a single grinding mill 604 ', coupled with three separators 608'a, 608'b, 608'c arranged in series to provide triple classification of the milled material 606 ', with the first, second and third thick fractions 612'a, 612'b, and 612'c recycled back to the mill 604'. For example, a VRM, modified to include two high efficiency classifiers coupled with the initial separator around the perimeter of the milling table, can provide triple classification, as shown in Figure 6F.
[0118] [0118] Figure 7A illustrates a manufacturing system 700 for processing material 702 which includes a coarse grinding circuit consisting of coarse mill 704 and first classifier 708a, which produces the first coarse fraction 712a, recycled back to the coarse mill 704, and the first fine fraction 710a, fed to the second classifier 708b. The second classifier 708b produces the second fine fraction 710b and the second thick fraction 712b, fed to the third classifier 708c to remove the fines, which provide the third fine fraction 710c, and produce the third thick fraction 712c, which is fed to the mill fines 714 of the fines grinding circuit which includes the fourth classifier 708d to classify the re-ground material 716. The fourth fine fraction 710d is combined with the second and third fine fractions 710b, 710c to produce the product 718. The fourth fraction coarse 712d is recycled back to the 714 fine mill.
[0119] [0119] Figure 7B illustrates the manufacturing system 720 that differs from system 700 in that the third fine fraction 730c is fed to the second classifier 728b to mix with the second fine fraction 730b to produce a current that is combined with the fourth fine fraction 730d to produce product 738. Figure 7C illustrates system 740 which differs from systems 700 and 720 in that both the third and fourth fine fractions 750c, 750d are fed to the second classifier 748b for mixing with particles fines within the second classifier 748b to produce the product 758. Figure 7D illustrates 760 which provides double classification for both coarse and fine grinding circuits and uses the second classifier 768b to produce the final product 778.
[0120] [0120] Figure 7E illustrates the system 700 'for separately processing the first material 702 and the second material 722' and then combining the resulting materials to produce the combined mixed stream 718 '. The first material 702 is processed by the first grinding device 704 'to produce the first initial milled product 706', fed to the separators 708'a, 708'b arranged in series, with the first coarse fractions 712'a, 712'b being recycled back to the first grinding device 704 '. The second material 722 'is processed by the second mill 724' to produce the second initial milled product 726 ', which is fed into the separators 728'a, 728'b arranged in series, with the second thick fractions 732'a, 732' b being recycled back to the second grinding device 724 '. The second processed material 730'b is fed to the classifier 708'b and combined with a first processed material to produce the final combined product 718 '.
[0121] [0121] According to one embodiment, a VRM or high pressure grinding cylinder is used to prepare the narrow PSD cement and / or one or more SCM fractions. Such mills may include a grinding bed and one or more high efficiency classifiers in series. A cylinder mill is configured to have a crushing profile, material residence time, and classifier efficiency to produce the narrow PSD cement. The cylinder mill has components and operating parameters selected to produce narrow PSD cement with minimal ultrafine particles and substantially less coarse particles, compared to conventional OPC. As an example, the components and operating parameters of a VRM selected to produce the narrow PSD cement include one or more obstruction ring height, air flow per mass, internal recirculation rate, external recirculation rate speed and / or air volume, classifier cut-off point, classifier capacity, classifier separation efficiency, grinding bed pressure, cylinder width, cylinder diameter, cylinder spacing, table speed, table geometry, geometry cylinder, material feed rate, grinding aid, and the like. IV. PREPARED CEMENT PRODUCTS USING SCM-CEMENT MIXTURES
[0122] [0122] Cement-SCM mixtures with compacted particles can be used in place of OPC, mixtures at the OPC and SCM site, intermittent mixtures, and other cements known in the art. They can be used as the exclusive or supplementary binder to prepare concrete, ready mix concrete, bagged concrete, bagged cement, mortar, bagged mortar, plaster, bagged plaster, molding compositions, or other new or dry cement compositions, known in technical. Cement-SCM mixtures with compacted particles can be used to manufacture concrete and other cement compositions that include a hydraulic cement, water and aggregate binder, such as fine and coarse aggregates. Mortar typically includes cement, water, sand, and lime and is hard enough to support the weight of a brick or concrete block. Oil well cement refers to cement compositions combined and continuously pumped into a well bore. Plaster is used to fill spaces, such as cracks or cracks in concrete structures, spaces between structural objects, and spaces between tiles. Molding compositions are used to make molded or cast objects, such as vases, tubs, posts, walls, floors, fountains, ornamental stone, and the like.
[0123] [0123] Water is both a reagent and a rheology modifier that allows a new cement composition to flow or be molded into a desired configuration. Hydraulic cement reacts with water, binds the other solid components together, and is most responsible for the initial development of resistance and can contribute to the further development of resistance. Mixtures with high PPD have reduced void space, which reduces water demand and increases handling for a given amount of water. V. EXAMPLES
[0124] [0124] The examples in WO 2011130482 are modified to produce cement-SCM mixtures in which at least a fraction of SCM and the narrow PSD cement fraction have MPSs that differ by a multiple of 3.0, 3.05, 3 , 1, 3.15, 3.2, 3.25, 3.3, 3.4, 3.5, 3.75, 4, 4.25, 4.5, 5, 5.5, 6, 6 , 5, 7, 7.5, 8, 8.5, 9, 9.5 or 10 to produce a cement-SCM mixture having a PPD of 57.0, 57.5%, 58%, 58.5, 59%, 59.5, 60%, 60.5%, 61%, 61.5%, 62%, 62.5%, 63%, 64%, 65%, 66%, 67.5%, 70% , 72.5%, 75%, 80%, 85%, or 90%. EXAMPLE 1
[0125] [0125] A cement-SCM mixture is prepared having the following components:
[0126] [0126] The PPD of the preceding mixture is greater than 57.0 (i.e., 60 or greater). EXAMPLE 2
[0127] [0127] A cement-SCM mixture is prepared having the following components:
[0128] [0128] The PPD of the preceding mixture is greater than 57.0 (i.e., 60 or greater). EXAMPLE 3
[0129] [0129] A cement-SCM mixture is prepared having the following components:
[0130] [0130] The PPD of the preceding mixture is greater than 57.0 (i.e., 65 or greater). EXAMPLE 4
[0131] [0131] A cement-SCM mixture is prepared having the following components:
[0132] [0132] The PPD of the preceding mixture is greater than 57.0 (i.e., 65 or greater).
[0133] [0133] Any of Examples 2-4 are modified to create separation between the d99 of a minor fraction and the d1 of the next major fraction, to further increase the PPD.
[0134] [0134] The present invention can be embodied in other specific forms, without leaving its spirit or its essential characteristics. The described modalities are to be considered, in all aspects, only as illustrative and not restrictive. The scope of the invention is therefore indicated by the appended claims, rather than by the preceding description. All changes that fall under the meaning and equivalence range of the claims are to be included in its scope.

权利要求:
Claims (15)
[0001]
Mixture of cement-supplementary cement material (SCM), CHARACTERIZED by the fact that it comprises: a fraction of narrow particle size distribution (PSD) hydraulic cement having a PSD defined by a lower end point of the PSD, average particle size, and an upper end point of the PSD; and at least a fraction of SCM having a PSD defined by a lower end point of the PSD, average particle size, and an upper end point of the PSD that differ from the lower end point of the PSD, the average particle size, and the upper end point of the PSD of hydraulic cement fraction, wherein at least a fraction of SCM having an average particle size that differs from the average particle size of the narrow PSD cement fraction by a multiple of 3.0 or more for the cement-SCM mixture to form a slurry of cement, when initially mixed with water, having a maximum particle compaction density of at least 57.0%.
[0002]
Cement-SCM mixture, according to claim 1, CHARACTERIZED by the fact that the cement-SCM mixture forms a cement paste, when initially mixed with water, having a maximum particle compaction density of at least 60%, more preferably at least 65%, and most preferably at least 70%.
[0003]
SCM-cement mix according to claim 1, CHARACTERIZED by the fact that the SCM-cement mix comprises a fraction of fine SCM having an average particle size so that the average particle size of the hydraulic cement fraction is at least 3.0 times the average particle size of the fine SCM fraction and a thick SCM fraction having an average particle size that is at least 3.0 times the average particle size of the hydraulic cement fraction.
[0004]
SCM-cement mix according to claim 3, CHARACTERIZED by the fact that the average particle size of the hydraulic cement fraction is at least 3.5 times the average particle size of the fine SCM fraction and / or the size The average particle size of the coarse SCM fraction is at least 3.5 times the average particle size of the hydraulic cement fraction.
[0005]
Cement-SCM mixture according to claim 3, CHARACTERIZED by the fact that the average particle size of the hydraulic cement fraction is at least 4 times the average particle size of the fine SCM fraction and / or the particle size The average fraction of the thick SCM fraction is at least 4 times the average particle size of the hydraulic cement fraction.
[0006]
SCM-cement mixture, according to claim 3, CHARACTERIZED by the fact that: the narrow hydraulic cement fraction of PSD has a d90 in a range from 8 µm to about 35 µm and a d10 in a range from about 1.0 µm to about 15 µm; the fine SCM fraction has a d90 less than about 15 µm; and the coarse SCM fraction has a d90 in a range of about 30 µm to about 300 µm.
[0007]
SCM-cement mixture, according to claim 3, CHARACTERIZED by the fact that: the narrow hydraulic cement fraction of PSD has a d90 in the range of 10 µm to about 30 µm and a d10 in the range of about 1.25 µm to about 12 µm; the fine SCM fraction has a d90 less than about 10 µm; and the fraction of thick SCM has a d90 in a range of about 40 µm to about 200 µm.
[0008]
Cement-SCM mixture according to claim 3, CHARACTERIZED by the fact that the cement-SCM mixture additionally comprises a third fraction of SCM having an average particle size that is at least 3.0 times the average particle size of the fraction of thick SCM.
[0009]
Cement-SCM mixture, according to claim 1, CHARACTERIZED by the fact that hydraulic cement and at least a fraction of SCM are processed and mixed without interruption.
[0010]
Method of making a cement-SCM mixture, as defined in claim 1, CHARACTERIZED by the fact that it comprises: supply a narrow particle size distribution (PSD) hydraulic cement; and mixing the narrow PSD hydraulic cement with at least one supplementary cement material (SCM) to form the cement-SCM mixture.
[0011]
Method according to claim 10, CHARACTERIZED by the fact that the narrow PSD hydraulic cement is processed using one or more of a high pressure grinding cylinder in combination with air classification, vertical cylinder mill, bar mill, press cylinder, ball mill, hammer mill, jet mill, dry ball mill, or ultrasonic grinding mill, alone or in combination with one or more of a high efficiency classifier or sieve.
[0012]
Method according to claim 10, CHARACTERIZED by the fact that at least one SCM is processed using one or more of a vertical cylinder mill, bar mill, press cylinder, ball mill, hammer mill, hammer mill, jet, dry ball mill, or ultrasonic grinding mill, alone or in combination with one or more of a high efficiency classifier or sieve.
[0013]
Method according to claim 10, CHARACTERIZED by the fact that it additionally comprises mixing at least one of fine aggregate, coarse aggregate, water, or chemical adjuvant with hydraulic cement and at least one SCM.
[0014]
Cement composition, CHARACTERIZED by the fact that it comprises: a cement-SCM mixture as defined in claim 1; and at least one of fine aggregate, coarse aggregate, water, or chemical adjuvant.
[0015]
Cement composition according to claim 14, CHARACTERIZED by the fact that the cement composition comprises freshly mixed or hardened concrete.

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同族专利:

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公开号 | 公开日

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EP2768788A4|2015-09-09|

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BR112014009653A2|2017-05-09|

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US9238591B2|2016-01-19|

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PE20142096A1|2014-12-06|

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US20140224154A1|2014-08-14|

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MX2014003888A|2015-02-10|

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EP3636615A1|2020-04-15|

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US20150144030A1|2015-05-28|

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CO6930350A2|2014-04-28|

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EP2768788A1|2014-08-27|

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WO2013059339A1|2013-04-25|

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EP2768788B1|2019-12-04|

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CN104010988B|2016-04-13|

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US8974593B2|2015-03-10|

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CN104010988A|2014-08-27|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-04-07| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-11-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-01-12| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161549742P| true| 2011-10-20|2011-10-20|

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US61/549,742|2011-10-20|

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PCT/US2012/060640|WO2013059339A1|2011-10-20|2012-10-17|Particle packed cement-scm blends|

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