JPH0616035B2 - Quantitative measurement method for surface adsorbed liquid of granular material or fiber material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Object of the Invention" The present invention relates to a method for quantitatively measuring an adsorbed liquid on the surface of a granular material or a fibrous material. It is intended to provide a method capable of quantifying a liquid and measuring it accurately.

Industrial application Quantitative measurement of surface adsorbed liquid of granular material using granular material or fibrous material and liquid, or in a mixture of them and powder.

2. Description of the Related Art As a raw material for natural earth and sand and various chemical or physical industrial purposes, there are a wide range of aggregates of powder and granules, and water or other liquids may be attached or blended with these powders and granules. Many. For example, it is almost the case that moisture or the like is attached to the surface of naturally occurring earth and sand, etc., and a special treatment is required to bring it into a state where it is not attached at all. Further, in obtaining each product chemically or physically using a granular material, water and other liquids are often added and mixed (including kneading or kneading).

By the way, regarding the liquid such as water attached to the surface of the granular material, there are those that are held between the particles and are retained in a capillary manner and those that are adsorbed on the surface of the particles, the former is due to vibration and air pressure fluctuations. Although the latter can be said to exhibit a stable adhering state while being relatively easily detached, conventionally, these liquid components are generally understood as adhering or adsorbing liquid at the end, and It is qualitative even if it is considered as described above, and there is no specific method for quantitatively measuring the adsorbed liquid.

In addition, in the conventional general technical state as described above, the inventors of the present invention have disclosed in Japanese Patent Application No. 58-5216 (Japanese Patent Laid-Open No. 59-13).
1164) and Japanese Patent Application No. 58-245233 (Japanese Patent Application Laid-Open No. 60-139407), in particular, test measurement for quantification of adsorbed liquid on the surface of fine aggregate used for concrete or mortar or use thereof. One method was provided. That is, this prior application technology is to distinguish between the one that is simply retained and the one that has been adsorbed as described above, and in particular, to quantitatively test and measure the latter, adjusting the concrete or mortar, and improving the mixing stage. Has gained significant improvement.

Problems to be Solved by the Invention The conventional general techniques described above are qualitative, and it is difficult to accurately grasp the liquid content and control the liquid content accordingly. That is, it is often impossible to clarify the actual condition of the liquid content adhering to and contained in such a powder or granular material by simply adhering or containing the liquid due to the properties of the powder or granular material itself. Even if there is a concept of adsorbed water that is stably adsorbed on the surface of a particle, it is qualitatively understood, such as the surface dry saturated state shown in page 275 of the concrete dictionary, and the properties of cement, An accurate index cannot be sought for the concrete adjustment of concrete, etc., if it is qualitatively understood to the extent that it is considered to be affected by the type properties of aggregate, driving conditions, formwork conditions, weather conditions, etc. .

In addition, landslides caused by a large amount of water during rainfall, collapse due to fluidization of earth and sand during an earthquake, and other phenomena may occur due to a relatively small amount of rainfall, or may not occur due to a considerable amount of rainfall. It is not possible to obtain concrete collapse or construction conditions to prevent its occurrence.

It can be said that the technique of the above-mentioned prior application by the present inventors is not only effective in distinguishing between the adsorbed liquid on the particle surface and that not adsorbed, but also for quantitatively elucidating the adsorbed liquid, which is very effective. According to the results of adjusting concrete and mortar, which are specifically measured, each cement, there is a dislike that can not have appropriate accuracy without adjustment in the adjustment of concrete, that is, the present inventors As a result of detailed examination of such measurement results, it is indispensable for the measurement to form a state in which particles are brought into collective contact with each other, and in such a collective deposition contact state, adsorption retention at the contact point is observed. Since liquid is generated, it is difficult to accurately obtain the target adsorption liquid. Therefore, it is difficult to secure the control with sufficiently high accuracy.

"Structure of the invention" Means for solving the problems Measured by changing the ratio of a given powder such as fly ash, cements, slag powder, mud, clay or sludge to water and a given liquid to the said powder. Therefore, prepare a plurality of samples that are each mixed with granular materials or fibrous materials, perform dewatering treatment on each of these samples under constant processing conditions, and determine the liquid retention amount of each sample after these dewatering treatments. Obtained, the liquid retention rate of the powder from the respective liquid retention amount and the amount of each powder in each sample described above, the powder retention rate and the granular material or fibrous material zero state powder for each sample Granular material or fibrous material, characterized in that the ratio of the difference between the liquid retention rate and the granular material or fibrous material to the powder ratio in each sample is obtained as the surface adsorbed liquid rate of the granular material or fibrous material. Of surface adsorbed liquid Quantitative measurement method.

By mixing the working powder, the indirect point liquid of the granular material becomes the liquid retention amount for the powder.

The liquid holding amount of each sample after the liquid removal treatment was obtained for each of the plurality of samples with different ratios to the powder, and the liquid holding ratio for the powder was calculated from these liquid holding amounts and the respective powder amounts in each sample. can get.

The powder retentate in the zero state of the granular material for each sample corresponds to the metastable retentate at the indirect point of the particles, and the difference between the retentivity and the powder retentate ratio is the granularity in each sample. The ratio that changes depending on the change in the material or fiber material to powder ratio is obtained as the surface adsorption rate of the granular material or fiber material.

EXAMPLE The present invention as described above will be further explained. As a result of repeated studies and inferences made by the present inventors to improve the accuracy of the above-mentioned prior application technique, as shown in FIG. As a depositing liquid for various granular materials or fibrous materials (hereinafter typically referred to as granular materials), those retained in the voids between particles (Fig. (A): hereinafter simply referred to as (a)) and stable state on the particle surface Adsorbed on [Fig. (B):
In addition to (b)], the liquid component that is kept in a metastable state as a state in which two particles crotch between the particles and swell from the adsorbed liquid layer at the junction point between the particles [(c) in the figure: Simply
(c)), and in the actual measurement, unless the metastable retentate (c) at the junction is removed, it will be present individually in the cement paste such as mortar and concrete. It was presumed that a highly accurate quantitative adsorbent volume (b) was not required for the granular material.

Therefore, as a result of repeated research on measurement of the amount of adsorbent (b) excluding the metastable retentate (c) at such a junction part, for example, decompression treatment or fine grained material such as sand Even if dehydration treatment is performed by applying centrifugal force, etc., the metastable retentate (c) at the contact portion as described above cannot be properly removed unless it is dehydrated and dried to an absolutely dry state. If the surface-adsorbed liquid (b) does not remain in red when dehydrated and dried to an absolutely dry state as described above, the amount of the stable adsorbed liquid (b) cannot be obtained in any case. Therefore, after further study and research, it was clarified that the stable adsorption liquid could not be removed properly without removing the stable adsorption liquid. As a result of investigating how to obtain the amount of liquid (b), that is, pursuing a method that can be obtained as a value that appropriately removes the contact liquid component (c) As an auxiliary material, it was conceived to use a powder having a smaller particle size than the target fine-grained material. In other words, the slurry (or paste) formed in the mixed state of the granular material and the powder is used to determine the liquid holding amount after applying the predetermined liquid removing conditions. The liquid holding amount thus obtained is The surface adsorbed liquid (b) and the liquid equivalent to the contact liquid (c) will be included, but auxiliary material powder must be present in the part corresponding to the liquid contact (c). That is, it can be determined as a state in which the above-mentioned granular material indirect point portion liquid component (c) is replaced by the powder and the surface adsorption liquid for the powder.

By the way, it is natural that the target surface adsorbed liquid (b) amount cannot be obtained as it is with respect to the results obtained as described above. Therefore, in the present invention, the same mixed system of liquid and powder is used. Prepare a plurality of samples with different ratios of granules to powder, perform dewatering treatment on these samples under certain conditions, and obtain the liquid retention amount after each treatment. Is divided by the amount of each powder in the mixed system to calculate the liquid retention rate for the powder, and the gradient obtained by the liquid retention rate for these powder pairs and the powder-to-particle ratio in each sample described above is It is proposed that the particle be obtained as a surface adsorbent under the above-mentioned liquid removal treatment conditions.

Further, in the above-mentioned case, it is apparent that the liquid retention rate after the same dewatering treatment for the sample in which the mixing ratio of the granular material with respect to the mixed system is zero is obtained as the surface adsorption liquid of the powder under the dewatering treatment condition. .

As the above-mentioned granular material, not only fine aggregate such as sand, it is natural that granular materials in various industries can be adopted, but also silica fiber having a certain length, carbon fiber,
Various fiber materials such as metal fibers and glass fibers may be used. As the powder, Portland cement and other cements are used in the field of the concrete industry, but gypsum powder, slag powder, etc. may be used, and fly ash etc. may be used. Of course, mud, clay, sludge, etc. can be used to clarify the properties of natural soil layers. It is extremely significant to adopt glass spheres as the above-mentioned powder material, and this is not only formed into a true sphere by being dispersed in a molten state, but also liquid removal treatment using centrifugal force, for example. Under the conditions, it has the characteristic of being a standard granular material for carrying out the method of the present invention as described above, which can easily form the zero state of the surface adsorbed liquid.

Water is typically used as the above-mentioned liquid, but it may be alkalized or acidified by containing other chemical components in water, a dispersant, a water reducing agent, an air entraining agent, a surface-active agent, etc. There are those added, those containing viscous components, etc.,
Further, any substance containing an oil / fat component, an alcohol component, an ammonia component, or the like, and any substance such as an oil / fat component, an alcohol component, or the like that exhibits a liquid state at room temperature may be used.

Any method such as gravity, vacuum, or centrifugal force may be adopted for the liquid removal processing. However, under the gravity condition, it takes a considerably long time, and the treatment result is likely to be different between the surface layer and the lower layer. Alternatively, it is preferable to employ centrifugal force. The inventors of the present invention have also adopted Japanese Patent Application No. 51-147180 (Japanese Patent Application Laid-Open No. 53-71859) which uses reduced pressure conditions and Japanese Patent Application No. 58-245233 (Japanese Patent Application Laid-Open No. 60-245233) which uses centrifugal force. -139407
No.) has been proposed, and it can be said that these methods are advantageous for obtaining accurate results in a short time.

Further, as the granular material to be added to the paste or slurry prepared by the liquid and powder such as a certain amount of water as described above, especially with respect to sand having irregularities on the surface, an air layer is partially present on the surface. Forming and remaining causes fluctuations in the measurement results. The air layer attached in this way is difficult to remove even by kneading, especially in a viscous paste, and it is possible to obtain a highly accurate measurement result by removing the air layer attached to the surface by moistening it well before charging. It is preferable above. Of course, it is advantageous to adjust the surface adhering liquid rate after removing the surface adhering air layer to be constant, and for this purpose, the velocity energy according to the present inventors' proposal is also adjusted. Japanese Patent Application Sho 54-
It is suitable to employ methods such as 147628 (JP-A-56-73518) and Japanese Patent Application No. 58-167513 (JP-A-60-58808). If there is no such equipment, for example, 24
You may make it dehydrat by making gravity act for a long time like time or more.

The above-mentioned Japanese Patent Application No. 58-245233 proposed by the inventors of the present invention as being capable of imparting the same liquid removal treatment conditions to a plurality of samples within a relatively short time.
No. 19407), the specific gravity is 2.90, the specific surface area is 3790 cm ² / g, and the specific gravity is 2.90.
The results of dehydration treatment under various centrifugal force conditions by using a fly ash with a specific surface area of 3080 cm ² / g in No. 19 are summarized in Fig. 5, and the centrifugal force for the dehydration treatment is high. Adsorbed water film thickness (t) after treatment according to
Is confirmed to be small.

The accuracy of the measurement is proportional to the centrifugal force, and the reason why the centrifugal force as high as possible acts on it is to improve the accuracy. On the other hand, increasing the centrifugal force in this way increases the energy consumption for measurement. It is obvious that the centrifugal force is 1 g or more, preferably 2 g or more, and the time is 1 minute or more, preferably 2 minutes, taking into consideration the measurement accuracy required in each case. It is preferable to perform the liquid removal treatment using the above conditions.

The results of the measurements performed by the inventors on the ordinary blast furnace slag powder, the ordinary Portland cement, the medium heat cement, and the fly ash after the dewatering treatment for 30 minutes each due to the centrifugal force change are shown in Table 1 below together with the physical properties thereof. It is as summarized.

The specific processing of the method of the present invention as described above will be further described to clarify the industrial operation and effect of the method of the present invention. That is, the surface adsorbed liquid is the smallest as the granular material or the fine aggregate as described above, and the glassy spheres that are supposed to be almost zero when the liquid removal treatment by the centrifugal force as described above is performed, Adopting sand such as river sand, which is clear that surface adsorbed water is more than that, and considering the case where the test measurement is performed by applying the constant centrifugal force as described above, the vitreous sphere field is A kneaded product of water obtained by variously changing the ratio of the sample aggregate (S) to the powder (F), and the surface adsorption of the glassy spheres in the kneaded product having a certain volume. It is clear that the amount of powder (F) having adsorbed water is relatively small if the amount of aggregate (S) having a low water ratio is sequentially increased. That is, in such a case, the water retention amount (W _Z ) of the kneaded material is inversely proportional to the aggregate-to-powder ratio (S / F),
The water retention rate ( _WZ / F), which is a value obtained by dividing the water retention amount ( _WZ ) by the powder amount (F), should be in a constant state.

On the other hand, when fine aggregates such as various sands that have a certain amount of surface adsorbed water are used as granular materials, the water retention rate of the powder is the same under the dehydration treatment conditions. If so, the water retention rate after treatment is the same,
The water adsorbed by the aggregate is retained on the surface of the aggregate, and the water retention amount after the dehydration treatment as the mixture increases in proportion to the amount of the aggregate. Therefore, when the water retention after the same dehydration treatment conditions was calculated for the same powder and the same amount of sample, the aggregate with a certain amount of surface adsorbed water was larger than the case of glass spheres with zero surface adsorbed water. The water retention amount is taken, and the surface adsorbed water ratio of the aggregate can be obtained by dividing the difference in the water retention amount thus obtained by the amount of the aggregate compounded in the mixture. It is presumed that the surface adsorbed water rate of such an aggregate is constant even if the aggregate-powder ratio in the mixture used changes.

A specific example of measurement according to the present invention is as follows.

Measurement example 1. Diameter is 0.3-0.6mm, unit volume weight is 1563kg /
m ³ and volume ratio of 63.8%, glass spheres having values close to those of naturally occurring sand in these figures, and fly ash with a specific gravity of 2.19 and a specific surface area of 3080 cm ² / g. Use the fly ash (F) and water (W ₁ )
Adjusted water, fly ash ratio (W ₁ / F)
Of 35% is prepared, and the mixture ratio of fly ash (F): glass spheres (B) is within the range of 1: 0.5 to 1: 2.5. 0.
Five types of mixtures were prepared, which were changed every 5%.

However, the proposal by the inventors of the present invention as to each of these mixtures has been made, and Japanese Patent Application No. 245233/58 (Japanese Patent Application Laid-Open No. 60-1) capable of uniformly dehydrating this kind of fine aggregate within a short time.
39407), the radius of gyration is 17.7 cm.
Using a mechanism in which a closed container containing absorbent cotton is arranged on the peripheral side of a rotating body rotating with a filter, that is, each sample is stored in these closed containers, and the liquid components separated by the rotating centrifugal force are used. Was subjected to a dehydration treatment with equipment so that the absorbent cotton was absorbed through the filter.
That is, the rotation is 1488 rpm, and the centrifugal force is 438 g.
The dehydration treatment (g is gravity) was performed for 30 minutes. It goes without saying that the above-mentioned five types of samples are, together with the sample in which the glass spheres are not mixed, enclosed in a container to which centrifugal force is applied and subjected to exactly the same centrifugal force dehydration treatment. Separately from this, Sagami River sand (unit volume weight 1611 kg / m ³ actual rate 64.3%, surface dry specific gravity 2.58, absolute dry specific grain 2.50,
Using FM 3.2), the same mixing ratio as that of the above glass spheres was set to 5 types of 1: 0.5 to 1: 2.5, and dehydration treatment was performed under the same conditions.

The initial water content is shown in Table 2 below.

As a result of the treatment as described above, W _S (in the case of Sagami River sand) and W _B regarding the water retention amount (g) after centrifugal force dehydration treatment
Their water retention capacity with (case of the glass bulb) (g) and water retention rate of the powder (F) from the amount of powder in each sample (W S _{/ F} or W _{B /} F:%) was determined The results are shown in Table 3 below. That W _S value or W _B values each corresponding variation for are shown, for the water retention rate to the powder, but not know the definite numerical value enough to grasp the general trend is for W S _{/ F} , W _B / F
As a result, a value of about 13% was obtained for all the samples.

By the way, it is Fig. 1 that summarizes the results of Table 3 in the form of a graph, and shows a very orderly result. From the results of Fig. 1, the water retention rate and zero powder are shown for each sample. The difference from the powder water retention in the state (no mixing of sand and glass spheres) can be determined to be about 13% from this chart. It should be noted that about 13% is about W in the case of the measurement result using the glass sphere as described above.
_Although it follows the above-mentioned value of _B / F, this is because the glass sphere has a very small surface adsorbed water rate (the water absorption rate by the flow cone is 0.048%). However, the one according to the present invention does not necessarily require the use of glass spheres having a remarkably small surface adsorbed water ratio as described above, and if different fine particles such as sand are used, as shown in FIG. As long as the value of W _S / F at the portion where the mixing weight ratio is 0 in the chart is the same as that of the powder used, it is as will be clarified in the measurement example described later that they substantially match.

From the results shown in FIG. 1 thus obtained, the water retention of the powder in the zero particle state and the particle-to-powder ratio (S / F or B / F)
Thus, the gradient θ formed on the chart as shown in FIG. 1 can be obtained as the surface adsorbed water rate of the granular material under the above-described dehydration treatment condition. In this measurement example, W _B
A powder water retention rate of the granules zero state of the with a, therefore the particulate material (Aiji river sand) surface adsorption of water ratio of {(W _S -W _B)
/ S × 100} is obtained as shown in the rightmost column of Table 2, and its average value is 3.60%.

Measurement Example 2. Portland cement was used as a powder, and the same glass sphere as in Measurement Example 1 was used together with silica sand (K), mountain sand (H), Oigawa sand (O) and Sagami river sand (S) with a cement-to-sand ratio ( C: S) ranges from 1: 0 to 1: 2.0.
Samples addressed to 5 types, each of which had a difference of 5, were prepared. As for Portland cement, the same bag was used for Oigawa sand and Sagamigawa sand, but other bags were used for different bags.

Let W be the amount of water, W _{Z be} the total amount of water retained after the dehydration process, W _{o be the} amount of water retained after the dehydration process in powder units, wz be the amount of water retained after the dehydration process in which the granular material is constrained, and β be the granularity The amount of water adsorbed on the surface of the material and the amount of water separated by dehydration treatment are used for BF.
Using θ as shown in FIG. 1, the following regression equation is obtained.

Further water distribution formula Is When the above formula is transformed, However, when the surface adsorbed water rate after dehydration treatment calculated by this equation is β'and it is shown together with the above measurement results, it is as shown in Table 4 below.

Further, the results are summarized as shown in Fig. 2. In the case of this measurement example, the results obtained by using Portland cement with Oigawa sand and Sagamigawa sand with other bags in different bags , Because of the difference in the quality of their cement, S
Although the value of W _Z / C at the position of / C = O is 2 groups, it is still around 16.05% and 18.5%.
It is clear that the values are almost the same in the vicinity.

Measurement Example 3 Using the same Sagami River sand having a specific gravity (ρs) of 2.5 and a diameter adjusted to 0.3 to 5 mm, a specific gravity (ρc) of 3.16 and a specific surface area (Sm) of this granular material 3340 cm ² / g Portland cement, specific gravity (ρ _E ) 2.90 and specific surface area 3
Highly accurate results can be obtained by using three types of powder, 790 cm ² / g blast furnace slag powder (Essent), and specific gravity (ρ _F ) 2.19 and specific surface area 3080 cm ² / g fly ash (F). With a centrifugal force of 438 g (1488 rpm), 30
The measurement results after the treatment for 1 minute are shown in Table 5 below.

Further, a summary of such measurement results is shown in FIG. 3. In FIG. 3, (A) shows the weight ratio and (B) shows the volume ratio. The results will vary depending on the body, and it is recognized that this is due to the affinity or familiarity between the powder and the granular material, and therefore, it is specifically measured using the granular material or the powder itself used in each case. Preferably.

"Effects of the Invention" In the case of the present invention as described above, it is possible to accurately measure the surface adsorbed liquid of fine aggregates and other granular materials quantitatively and appropriately eliminate the influence of contact liquid. It is possible to appropriately determine the compounding relationship in various industries using these granular materials, and it is possible to obtain the target product with less variation and excellent characteristics, so that the industrial effect It is a great invention.

[Brief description of drawings]

The drawings show the technical contents of the present invention. FIG. 1 is a chart summarizing the measurement results of Measurement Example 1 according to the present invention, and FIG. 2 is a chart summarizing the results of Measurement Example 2.
Fig. 3 is a chart summarizing the measurement results of Measurement Example 3, Fig. 4
The figure is an explanatory view showing the state of liquid components on the surface of the granular material or in the vicinity thereof in stages, and FIG. 5 is a dehydration treatment under various centrifugal force conditions by the present inventors using blast furnace slag powder and fly ash having different particle sizes. It is the chart which summarized and showed the result.

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Claims (7)

[Claims] 1. A granular material or a fibrous material to be measured by changing a ratio of a predetermined powder such as fly ash, cements, slag powder, mud, clay or sludge and water or another predetermined liquid to the powder. Prepare a plurality of mixed samples, perform the dewatering treatment under constant processing conditions for each of these samples, and obtain the liquid retention amount of each sample after these liquid removal treatments. The liquid retention rate for each powder is obtained from the amount of each powder in each sample described above, and the difference between the liquid retention rate and the powder to liquid retention rate of the granular material or the fibrous material zero state for each sample is respectively. Quantitatively the surface adsorbed liquid ratio of the granular material or the fiber material, which is obtained as a ratio of the surface adsorbed liquid ratio of the granular material or the fiber material in the sample Measurement method. 2. A liquid retention rate for each powder is obtained from the liquid retention amount of each sample obtained after the liquid removal treatment and the amount of powder in the sample, and the liquid retention rate and the granular material for each sample or The difference between the powder retention rate of the fibrous material zero state and the granular material or fibrous material in each sample is formed with the change of the powder-to-powder ratio. The method for quantitatively measuring the surface adsorbed liquid ratio of a granular material or a fibrous material according to claim 1, which is obtained as an adsorbed liquid ratio. 3. W is the amount of water, C is the amount of powder, S is the amount of granular material or fiber material, Wo is the liquid holding amount after the liquid removal treatment in powder units, and BF is the liquid removal treatment. The method for quantitatively measuring the surface adsorbed liquid ratio of the granular material or the fiber material according to claim 1, wherein the surface adsorbed liquid β of the granular material or the fiber material is obtained by the following equation as the amount of water separated. 4. The method for quantitatively measuring the surface adsorbed liquid ratio of a granular material or a fibrous material according to claim 1, wherein centrifugal force is used as the dehydration treatment condition. 5. The granular material according to claim 1, wherein the peripheral surface of the granular material or the fibrous material is sufficiently moistened, and the granular material or the fibrous material is mixed in a mixing system of powder and liquid so that an air layer does not remain on the surface. Alternatively, a quantitative measurement method of the surface adsorbed liquid ratio of the fiber material. 6. The same deliquoring treatment is performed on a mixed system of a powder and a liquid in which no granular material or fibrous material is mixed, and the liquid retention rate of the mixed system after the deliquoring treatment is mixed under the above deliquoring treatment conditions. The method for quantitatively measuring the surface adsorbed liquid ratio of a granular material or a fibrous material according to claim 1, which is obtained as the surface adsorbed liquid ratio of the in-system powder. 7. The method for quantitatively measuring a surface adsorbed liquid of a granular material or a fibrous material according to claim 1, wherein the same powder as that used in each case is used as the powder.