JPWO2006059809A1 - Sample processing system for pore measurement - Google Patents

Abstract

The present invention can measure the surface, internal structure, and pore structure that accurately reflects the progress of the reaction such as hydration reaction at a specific time point as compared with the conventional pore measurement sample. It is an object of the present invention to provide a novel pore measurement sample, a novel production method and production apparatus for the pore measurement sample, and a novel pore measurement method and pore measurement apparatus using the measurement sample. . (1) a step of rapidly cooling the sample containing water taken out as a sample to a temperature not higher than the temperature at which the reaction substantially stops, and freezing the contained water, (2) A sample for pore measurement is obtained by a step of vacuum freeze-drying the specimen, (3) and a step of returning the obtained measurement sample to a normal temperature and normal pressure environment.

Description

The present invention relates to a measurement sample, a measurement sample production method and production apparatus, and a measurement method and measurement apparatus using the measurement sample.
The present invention also relates to a sample for pore measurement, a method and apparatus for producing a sample for pore measurement, and a measurement method and apparatus using the sample for pore measurement.

The present invention is a measurement sample that can be used in various measuring methods and measuring apparatuses, and a pore measurement sample that can be used for pore measurement.
Various materials are known for measurement samples and pore measurement samples that can be used in various measurement methods and measuring devices. The following is a hardened concrete body as a measurement sample and pore measurement sample. A specific example will be described.
In concrete, after ready-mixed concrete is placed in a mold, a hydration reaction proceeds and curing progresses to exhibit a predetermined strength and durability.
Here, the hydration reaction refers to a reaction between cement and water. Hydrate (mostly fine particles of 0.1 μm or less) precipitated on the surface of cement powder particles (0.2 to 100 μm) from the suspended state of cement clinker mineral when cement is mixed with water is unhydrated cement particles After the state of bonding, the voids are further filled by precipitation of hydrates, gradually strengthening the strong bond and curing to develop the strength. In Portland cement, the reaction of alkali, trilime aluminate, tetraaluminum iron aluminate, and gypsum was the primary reaction, and gradually alit (trilime silicate) and then berit (solid solution of dilime silicate) were hydrated and cured. (Non-Patent Document 1).
If there is a low temperature, drying, or rapid temperature change in the middle of the hydration reaction, the progress of the hydration reaction is hindered, and the intended result in terms of strength and durability cannot be obtained. For this purpose, curing is performed until a product having a predetermined strength is obtained. Therefore, the curing is an important work in the construction work, and whether or not the work is sufficiently performed results in the quality of the structure and the like. Originally, the hardened cement body has a pore structure, and the pores change with the progress of hydration. By examining the condition of the pores of the hardened cement body, it is possible to understand whether curing is properly performed, in other words, whether hydration is proceeding properly. Therefore, examining the pores of the hardened cement body is an important measurement item.
Deterioration due to salt damage and neutralization of concrete structures has become a social problem. The pore space of concrete is closely related to durability, water tightness and air permeability due to frost damage, salt damage, neutralization, etc. of concrete. From this, it is possible to judge the state of deterioration by cutting out a portion of the concrete to be inspected and examining the pore voids, and therefore examining the pore voids is an important measurement item.
Conventionally, various measurements and pore measurements are made on cement paste or concrete obtained by kneading cement with water, and the performance and state at that time are measured. In this case, in order to accurately perform the above measurement, it was necessary to measure the surface or internal state, the shape and distribution of the pores in a state where the hydration reaction was stopped. In order to stop this hydration reaction, it has been carried out to keep the sample in a dry state from the idea that it is necessary to make a state in which no water exists. Specifically, when various measurements are performed using a cement measurement sample, the cement measurement sample is cut out and kept at 105 ° C. or higher in order to obtain a measurement sample in that state. After the moisture contained in the sample is evaporated, the surface, internal structure, shape and distribution of pores are measured (hereinafter also referred to as a drying method).
However, this drying process does not substantially stop the hydration reaction, and the hydration reaction continues. Therefore, the measurement results of the surface and internal structure and the shape and distribution of the pores are hydrated. The state in which the reaction is proceeding will be measured. In addition, the pores may be deformed or damaged during the drying process, and an accurate result was not displayed. It has also been pointed out that if the drying is too strong, dehydration or shrinkage of the hydrate occurs, and the exact state may not be measured.
As a method for preparing a cement measurement sample, a stored sample is pulverized to 5 mm or less, and this sample is immersed in acetone, which is generally used as a solvent, and water contained in the cement measurement sample is washed with acetone. Substituting and suppressing the hydration reaction of the sample by leaving it in the absence of water, and then removing the acetone by vacuum drying the sample containing acetone, thereby completely removing the water. And measuring the surface and internal structure of the sample and the shape and distribution of the pores (hereinafter also referred to as D drying method (DD method)).
Even in this case, the surface and internal structure in a state not containing moisture contained in the sample, the method for measuring the shape and distribution of the pores is a good method and has been considered to be a standard method. Actually, there are problems of the degree of hydration suppression due to acetone substitution and the deformation and damage of the sample, and relative comparative measurement values can be obtained, but accurate measurement values cannot be obtained. It is also pointed out that drying is too strong and there is dehydration and shrinkage of hydrates.
In addition, a method of sucking acetone with an aspirator, a method of drying at 40 to 50 ° C., a method of drying at RH 11%, and a method of using isopropyl alcohol in place of acetone have been proposed. The result is similar to that of, and the result is not satisfactory.
According to the above conventional method, it is also reported that when a part of a cement paste or a concrete structure is cut out as a sample to measure pores, an accurate measurement value cannot be obtained (non- Patent Documents 2 and 3). In addition, this indicates that accurate measurement values cannot be obtained with respect to the measurement of the surface and internal structure according to the conventional method.
For this reason, it is measured when processing samples for pore measurement, such as cement paste, mortar, concrete and other cement-based mixtures that have not yet solidified, or cement mixtures that have already hardened and hydrated mixtures such as lime mixtures. There is a need for a sample manufacturing method that measures the state of pores that can accurately measure the degree of progress of the hydration reaction at the time, and the sample pores are not subject to deformation or damage, and the sample manufacturing Development of a method, an apparatus for producing a sample for measuring pores, a method for measuring pores using the sample for measuring pores, and a measuring apparatus has been eagerly desired.
Tokyo Chemical Doujin "Chemical Dictionary" page 1184 “Cement Hardened Materials Research Committee Report” pages 273-290 (2001) Japan Cement Association “Cement and Concrete” 684 2000. February, p. 52

An object of the present invention relates to a measurement sample, a novel measurement capable of measuring a state or structure that accurately reflects the progress of a reaction at a specific time point as compared to a conventional measurement sample Sample, a new method for manufacturing the fixed sample and a manufacturing apparatus therefor, and a new measurement method and apparatus using the new sample.
In addition, regarding the sample for pore measurement, compared to the conventional sample for pore measurement, the surface, internal structure and pore structure that accurately reflect the progress of the reaction such as hydration reaction at a specific point in time. Provided are a novel pore measurement sample that can be measured, a novel production method and production apparatus of the pore measurement sample, and a novel pore measurement method and pore measurement apparatus using the measurement sample It is to be.
The present inventors diligently researched on the above problems and found the following to complete the present invention.
In the sample by the conventional D drying method or the like, as described above, the water contained in the sample is suppressed by hydration reaction by substituting water and acetone by immersing the sample in acetone, and then vacuum-dried in a desiccator. Thus, acetone is removed. Thus, in the measurement of the pores subjected to the treatment for replacing water with acetone, a satisfactory result is not necessarily obtained. The cause is that even if the treatment for replacing water with acetone is performed, water still remains, and the hydration reaction has not been sufficiently suppressed. As a result, it is considered that the hydration reaction could not be stopped. Also, in the vacuum drying process, it is thought that water can be evaporated almost completely, but even if the hydration reaction is stopped at this stage, the hydration reaction has already proceeded. This is considered to be a state that does not reflect the exact progress of the hydration reaction.
When measuring the progress of the hydration reaction by the conventional method, the present inventor cannot stop the hydration reaction by any means to completely remove the water contained in the sample. As a result, a time delay required for the hydration reaction occurs, which does not accurately reflect the progress of the hydration reaction. Then, even if there existed water, I thought that an exact state could be measured by making the hydration reaction into a stopped state.
In order to stop the hydration reaction, it is considered that the problem can be solved if an absolute 0 degree state can be realized. Actually, the cement is rapidly cooled to -10 ° C. or lower to freeze the moisture, and then the two methods of vacuum lyophilization with the moisture frozen are combined (hereinafter also referred to as FD method). For example, the progress of the hydration reaction at the time of the rapid cooling can be stopped, and as a result, the pore structure reflecting the state where the hydration reaction at the specific time is stopped is measured. As a result, the present invention has been completed. And based on this result, it was also confirmed that the age, cement water ratio, and the relationship between various cements and compressive strength can be supported.
The specific processing content for that is as follows. The sample containing water taken out as a measurement sample is rapidly cooled to below the temperature at which the reaction substantially stops or below −10 ° C., which is the temperature at which the reaction stops substantially. The sample in a state where the water is frozen after being frozen is freeze-dried in a vacuum to remove the water. The preparation of the measurement sample is completed by the above-described freezing treatment, and it can be taken out and used as a sample.
The sample at the stage where the preparation of the sample is completed is kept at a low temperature and in a vacuum state. When using a sample, it is customary to use the sample at normal temperature and pressure. Considering the use of a sample at room temperature and normal pressure, a sample kept in a vacuum at a low temperature can be used at a temperature above the ambient temperature condition without changing the physical and chemical state of the sample. If processing is performed at room temperature and normal pressure, the state before using the sample is perfect. The treatment for this is carried out by allowing an inert gas to be present and filling, and simultaneously heating the sample to bring it to a normal temperature and normal pressure state in which the sample is used. Without performing this operation, if the sample is taken out under a temperature condition below ambient temperature under normal temperature and pressure, the surface of the sample is subject to changes due to the atmosphere, and the sample surface may change. Specifically, when moisture is contained in the atmosphere, moisture adheres to the surface of the sample and condensation occurs, resulting in a physical or chemical change of the sample. This treatment can be performed as an operation before the sample is used after the sample is prepared, or can be performed by being incorporated in an operation of a series of sample preparation methods.
According to the present invention, the following inventions are provided.
(1) Concerning the measurement sample, the water-containing sample taken out as the measurement sample is rapidly cooled below the temperature at which the reaction substantially stops, the contained water is frozen, and the water is subsequently frozen. A sample for measurement, which is obtained by lyophilizing a sample in a dry state to remove moisture.
(2) The sample containing moisture taken out as a measurement sample is a hardened cement, and the temperature at which the reaction substantially stops is −10 ° C. or less. .
(3) A measurement obtained by heating the sample while filling the measurement sample according to (1) or (2) in the presence of an inert gas to bring it to a state of normal temperature and pressure. Sample.
(4) Concerning the measurement sample, the water-containing sample taken out as the measurement sample is rapidly cooled below the temperature at which the reaction substantially stops, the contained water is frozen, and the water is subsequently frozen. The sample in a vacuum is freeze-dried to remove moisture, and the sample from which the moisture has been removed is heated to a state of normal temperature and pressure by heating the sample while filling it in the presence of an inert gas. A measurement sample characterized by being obtained.
(5) A sample containing moisture taken out as a measurement sample is a hardened cement, and the temperature at which the reaction substantially stops is −10 ° C. or less, and the sample in a state where moisture is subsequently frozen is − Moisture is removed by lyophilization under vacuum at a temperature of 10 ° C. or lower, and the sample from which the obtained moisture has been removed is heated while being filled with an inert gas and brought to a normal temperature and normal pressure state. (4) The measurement sample according to (4).
(6) With respect to the measurement sample, the sample containing the water taken out as the measurement sample is rapidly cooled to a temperature that substantially stops the reaction in the vacuum freeze dryer, and the contained water is frozen. Subsequently, the sample in a state where the moisture was frozen was lyophilized in vacuum to remove the moisture, and the sample from which the moisture was removed was then heated in the presence of an inert gas, and the sample was heated to normal temperature and normal pressure. A measurement sample obtained by being in the state of
(7) A sample containing moisture taken out as a measurement sample is a hardened cement, and the temperature at which the reaction substantially stops is −30 ° C. or lower, and the sample in which moisture is subsequently frozen is − Water was removed by lyophilization under vacuum at 20 ° C. or lower, and the obtained water-removed sample was heated at 30 ° C. while being filled with an inert gas. (6) The measurement sample according to (6), which is obtained by making a state.
(8) A freezing apparatus and moisture that rapidly cools a sample containing moisture taken out as a measurement sample to a temperature at which the reaction substantially stops and freezes the contained moisture with respect to the measurement sample manufacturing apparatus An apparatus for producing a sample for measuring pores, characterized in that it comprises a vacuum freeze-drying apparatus for vacuum-freezing and drying a sample in a state of being frozen.
(9) The pore measurement according to (8), wherein the sample containing water taken out as a measurement sample is a hardened cement, and the temperature at which the reaction substantially stops is −10 ° C. or lower. Sample production equipment.
(10) The apparatus for producing a sample for pore measurement according to the above (8) or (9) is provided with an apparatus for heating the sample while being filled with an inert gas to bring it to a normal temperature and normal pressure state. An apparatus for producing a sample for pore measurement, characterized by comprising:
(11) A freezing apparatus that rapidly cools a sample containing moisture taken out as a measurement sample to a temperature at which the reaction substantially stops, and freezes the contained moisture, with respect to an apparatus for producing a pore measurement sample. , Vacuum freeze-drying device that removes moisture by vacuum freeze-drying the sample in a state where moisture is subsequently frozen, heating the sample while filling the obtained moisture-removed sample in the presence of an inert gas, An apparatus for producing a sample for measuring pores, characterized in that it comprises an apparatus for normal temperature and pressure.
(12) A sample containing water taken out as a measurement sample is a hardened cement, a freezing apparatus having a temperature at which the reaction substantially stops is -10 ° C. or lower, and a sample in which water is subsequently frozen. A vacuum freezing apparatus that removes moisture by vacuum lyophilization under conditions of −10 ° C. or lower, and the sample obtained by removing moisture is heated while continuing to fill in an inert gas, The apparatus for producing a sample for pore measurement according to (11), characterized in that the apparatus comprises a device under pressure.
(13) Concerning an apparatus for producing a sample for pore measurement, a sample containing moisture taken out as a sample for measurement is rapidly cooled and contained within a vacuum freeze dryer to a temperature that substantially stops the reaction. Freezing process for freezing water, followed by vacuum lyophilization of the sample in which the water has been frozen to remove the water, vacuum freezing process for removing the resulting water, and subsequent sample while filling with inert gas An apparatus for producing a sample for measuring pores, characterized in that a step of heating to a normal temperature and pressure state is performed.
(14) A sample containing moisture taken out as a measurement sample is a hardened cement, a freezing step in which the temperature at which the reaction substantially stops is −30 ° C. or lower, and a sample in a state where moisture is subsequently frozen A vacuum freezing step in which the water is removed by lyophilization under a condition of -20 ° C or lower, followed by a step of heating the sample at 30 ° C while filling it in the presence of an inert gas to bring it to a normal temperature and normal pressure state. The apparatus for producing a sample for pore measurement according to (13), characterized in that it is performed.
(15) A pore measurement method, comprising performing pore measurement using the measurement sample according to any one of (1) to (7).
(16) The method for measuring pores according to (15), wherein the method for measuring pores is a mercury intrusion method, and the pore distribution is measured.
(17) A pore measuring apparatus using the measurement sample according to any one of (1) or (7) in a pore measuring apparatus.
(18) The pore measuring device according to (17), wherein the pore measuring device is a mercury intrusion pore measuring device.
(19) The measurement sample according to any one of (1) and (7) above is applied to a spectroscopic analysis method, an X-ray analysis method, a structural analysis method, a surface analysis method, a thermal analysis method, a separation analysis method, an elemental analysis method, and A measurement method characterized by being used for the method according to any one of the EPMA methods.
(20) The measurement sample according to any one of (1) to (7) above, a spectroscopic analyzer, an X-ray analyzer, a structural analyzer, a surface analyzer, a thermal analyzer, a separation analyzer, an element analyzer, and A measuring device used for any one of the EPMA devices.
Compared with the conventional measurement sample, the measurement sample obtained in the present invention stops the hydration reaction occurring in the sample at the time of preparing the sample. It can be measured as a sample that accurately reflects the progress state. Thus, a new measurement sample that has not existed before can be obtained. If these measurement samples are used, they can be used in various methods and apparatuses for measuring the surface and internal structure.
In the case where the measurement sample is a hardened cement material, water is used in comparison with the conventional hardened cement material measurement sample used in the D drying method (DD method) for vacuum drying or the drying method for drying at 105 ° C. It is possible to accurately measure the surface, internal structure, and the state and structure of the pores at the time when the sum reaction is stopped and measurement is attempted. In addition, it is possible to accurately measure the progress of the hydration reaction of the hardened cement body. As a result, the age, cement water ratio, and the relationship between various cements and compressive strength can be supported.
Moreover, in this invention, the sample for cement hardening body pore measurement and its manufacturing method, the manufacturing apparatus of the sample for cement hardening body pore measurement, and the pore measuring method and measuring apparatus using the cement hardening body of this invention are obtained.

FIG. 1 shows a vacuum freeze dryer of the present invention.
FIG. 2 is a diagram showing procedures of the FD method and the D method.
FIG. 3 is a diagram showing the relationship between the freezing temperature and the temperature lowering property of the sample.
FIG. 4 is a diagram showing the drying property of a fine-grained sample by the FD method.
FIG. 5 is a diagram showing a comparative study of the drying property of the FD method with that of the DD method.
FIG. 6 is a diagram showing a measurement result by a low acceleration voltage image (SEM method).
FIG. 7 is a diagram showing the acetone immersion time and the result of mass measurement of the sample.
FIG. 8 is a graph showing the age pore volume and pore diameter distribution.
FIG. 9 is a diagram showing the pore size distribution with respect to age.
FIG. 10 is a diagram showing the relationship between the cement water ratio and the amount of pores.
FIG. 11 is a diagram showing the cement water ratio and the amount of pores.
FIG. 12 is a diagram showing the time required for temperature reduction to about −10 ° C. when the thickness (maximum width) of the sample is 40 mm.
FIG. 13 is a diagram showing the time required for temperature reduction to about −10 ° C. when the thickness (maximum width) of the sample is 100 mm.
FIG. 14 is a view showing an apparatus capable of performing the freezing step and the vacuum freeze-drying step in the same tank.
FIG. 15 is a view showing that a sample is manufactured through a freezing step, a vacuum freeze-drying step, and a normal temperature and normal pressure step by processing in a vacuum freeze-drying apparatus.
FIG. 16 is a diagram showing the results of measurement of temperature properties when performing a freezing step, a vacuum freeze-drying step, and a step of normal temperature and pressure in a vacuum freeze-drying apparatus.
FIG. 17 is a diagram showing changes in intensity when each drying time of a sample by NFD (FD method) and DD method is changed.
FIG. 18 is a diagram showing an observation result of SAME of NFD (FD method) 4h.
FIG. 19 is a diagram showing an observation result of SAME of NFD (FD method) 4h.
FIG. 20 is a diagram showing an observation result of SAME of NFD (FD method) 4h.
FIG. 21 is a diagram showing an observation result of SAME for NFD (FD method) 6 h.
FIG. 22 is a figure which shows the observation result of SAME of NFD (FD method) 6h.
FIG. 23 is a diagram showing an observation result of SAME for NFD (FD method) 6h.
FIG. 24 is a diagram showing the observation results of SAME of DD7d.
FIG. 25 is a diagram showing the observation results of SAME of DD7d.
FIG. 26 is a diagram showing the observation result of SAME of DD7d.
FIG. 27 is a diagram showing the observation results of SAME of DD14d.
FIG. 28 is a diagram showing an observation result of SAME of DD14d.
FIG. 29 is a diagram showing the observation results of the SAME of DD14d.
FIG. 30 is a diagram showing the observation results of SAME of DD21d.
FIG. 31 is a diagram showing the observation results of SAME of DD21d.
FIG. 32 is a diagram showing the observation results of the SAME of DD21d.
FIG. 33 is a diagram showing the observation results of SAME of DD27d.
FIG. 34 is a diagram showing the observation results of the SAME of DD27d.
FIG. 35 is a diagram showing the observation results of the SAME of DD27d.

Explanation of symbols

1: Vacuum freeze-drying chamber 2: Cold trap chamber 3: High vacuum pump 4: Drying shelf (three stages)
5: Temperature and pressure adjustment operation unit and recording device unit 11: Device for performing freezing step and vacuum freeze-drying step in the same tank 12: Drying shelf 13: Cold trap part 14: Temperature setting and adjustment operation device, pressure adjustment operation Device and recording device 15: vacuum pump and cooling pump storage part

The sample of the present invention is taken from a measurement object as a pore measurement sample or cut out. A sample for measurement can be used as long as the reaction is stopped and the state of the pores in that state is measured.
Taking the case of cement as an example, the object to be measured is cement paste, mortar, concrete, etc., a cement-based mixture that has not yet solidified or a cement mixture that has already hardened, and a hydrated mixture such as a lime mixture, etc. Means.
The cement paste is in a state where cement is kneaded with water. When the cement paste is left as it is, the cement paste is condensed and hardened due to the hydration action of the cement with time and generates strength.
The cement paste, also called cement mortar, is a mixture of cement and fine aggregate (sand) and kneaded with water. Sand, which is fine aggregate in aggregate, is cemented and cemented to generate strength. The ratio (weight) of cement: sand is in the range of 1: 1 to 3, and this ratio varies depending on the application.
The concrete is a mixture of cement, fine aggregate (sand), coarse aggregate (pebbles), and water in appropriate proportions, kneaded and mixed, or hardened. . The mixing ratio is usually 1: 2: 4 or 1: 3: 6. In some cases, admixtures are mixed in these. In concrete that requires strength and durability, the compressive strength is high, but the tensile strength is not so high, and reinforced concrete containing reinforcing bars is commonly used as the structure. Also, reinforce with reinforcing bars. A concrete mixer is a machine that mixes cement, sand, and pebbles with water to mix the concrete. The concrete produced by this concrete mixer is also included in the survey.
Cement mortar and concrete being cured for measurement, as well as cement mortar and concrete removed from the building, and fine aggregate (sand) and coarse aggregate (pebbles) contained in the concrete were removed. A sample is used. Of course, fine aggregate (sand) and coarse aggregate (pebbles) are not related to the measurement of pores, so even if they are removed, the measurement results are not affected significantly. Further, the sample collected in this way can be used as it is as a sample, but it can be used as a sample after having an appropriate volume shape.
Regarding the size of the sample, it can be used as an appropriate volume in consideration of subsequent operations, but it is not necessary to collect an unnecessarily large sample. If a fine particle having a diameter of 2.5 to 5.0 mm is used, there is no problem in the inspection.
The cement used can be any known cement, and is not particularly limited.
As for the cement to be used, specifically, ordinary Portland cement (density 3.16 g / cm ³ , specific surface area 3260 cm ² / g), early-strength Portland cement, blast furnace CB type, fly ash C type, eco C type, etc. Can be mentioned.
The measurement sample is a step of rapidly cooling a sample containing moisture, which is a partially cut measurement sample, to a temperature that substantially stops the reaction, and freezing the contained moisture (hereinafter, freezing step). It is obtained by a step of lyophilizing a sample in a state where moisture is frozen (hereinafter referred to as a vacuum lyophilization step).
When the sample containing moisture taken out as the measurement sample is a cement hardened body, the temperature at which the reaction substantially stops is −10 ° C. or less, and the step of freezing the contained moisture (hereinafter, freezing) The sample in which the moisture has been frozen is subsequently subjected to a process of removing the moisture by vacuum freeze drying (hereinafter referred to as a vacuum freeze drying process) to produce a sample for measuring a cement cement. be able to.
The freezing step and the vacuum freeze-drying step will be described below by taking the case of a hardened cement as an example.
Freezing process It is known that when cement is frozen below -10 ° C, the hydration reaction is virtually stopped (translated by Yoshiro Tokune, "Cement concrete chemistry for construction engineers", Gihodo, page 80 81 (issued in 1969)). This describes the temperature at which the hydration reaction of the cement stops, and this knowledge is used to stop the hydration reaction. It has not been conventionally performed to determine the degree of progress of the hydration reaction by measuring the state of the pores while the reaction is stopped.
In the freezing step, the progress of the chemical reaction of the sample is stopped at a certain point, and the state in which the progress of the hydration reaction at that point is stopped is stored and maintained. In a hardened cement or the like, in order to stop the hydration reaction of the sample, the sample, which is a sample, is rapidly cooled to -10 ° C. or less at which the hydration actually stops in advance from room temperature or in some cases from the outside temperature. It is a process. The temperature measurement of the sample is based on the result of measurement using a thermocouple including the following vacuum freeze-drying.
For young cement hardened bodies, it is as follows.
The temperature defines −10 ° C. or lower, but the temperature may be −10 ° C. or lower, and may be −20 ° C., −30 ° C., −40 ° C., or 40 ° C. or lower. It is not necessary to lower the temperature more than necessary, and in these cases, the effect can be sufficiently achieved. Of course, a temperature between the above temperatures, for example, between −10 ° C. and −20 ° C. may be a temperature in between, for example, −15 ° C. Further, even if this temperature is made lower than necessary, it is not that a special effect is obtained. The time to reach this temperature is important. By rapidly freezing to the said temperature, for example, -10 degrees C or less, a hydration reaction can be stopped practically at that time. “Abruptly” means as short as possible. The sample, which is a sample, is solid, and it takes a certain amount of time to cool the inside to the same temperature as the outside. Time needs to fully consider these phenomena. Thickness has an important meaning in the shape of this sample. And it was as follows when it was investigated how much time the center part of thickness will be cooled.
When the thickness (maximum width) of the sample as a sample is 10 mm, it takes about 7 to 8 minutes when the temperature is lowered to about −10 ° C. Even in the case of −20 ° C., −30 ° C., −40 ° C., or about 40 ° C. or less, the temperature can be lowered to about 7 to 8 minutes. If this time is about 10 minutes, it is not actually a problem.
When the thickness (maximum width) of the sample, which is a sample, is 40 mm, it takes about 25 minutes when the temperature is lowered to about −10 ° C. (FIG. 12).
When the thickness (maximum width) of the sample as a sample is 100 mm, it takes about 90 minutes when the temperature is lowered to about −10 ° C. (FIG. 13).
By arranging the above results as the relationship between thickness and time, it is possible to calculate the time required according to the thickness and the time for “abruptly”.
The apparatus for performing this freezing process is as follows.
A thermo-hygrostat or refrigerator capable of temperature adjustment (from 20 ° C. to −40 ° C.) for freezing can be used. In order to freeze, it is effective to send a gas having a freezing temperature for freezing.
About a vacuum freeze-drying process A vacuum freeze-drying process removes the water | moisture content in the state of ice from a frozen state, and makes it the state which does not contain a water | moisture content. Attempting to evaporate and remove the ice by heating it will result in a liquid phase (melting) under conditions of temperature and pressure above the triple point (temperature 273.15 K (0 ° C., pressure 633.3 Pa (4.6 ToRR)). It passes through the temperature (water state), then becomes a gas phase (passes the boiling temperature, water vapor), and is vaporized and removed. When evaporation / removal is performed by this route, the internal structure of the sample, which is a sample, is changed by the action of existing water. Specifically, it results in changing the state of the pores. On the other hand, under the temperature and pressure conditions below the triple point, the existing ice is sublimated and immediately becomes water vapor without going through a liquid state, and is evaporated and removed. Unlike the above case, there is no state of water, so there is nothing that changes the internal structure of the sample. As a result, the internal structure is stored without changing, and the internal structure and the pore structure can be measured without changing.
The state of evaporation / removal by sublimation is as follows. Sublimation latent heat, the heat necessary for sublimation, is supplied by radiation from the surface of the target sample and conduction from the bottom shelf, and passes through the dry layer present on the surface of the sample to the frozen layer present inside the sample. It arrives. And it is consumed as latent heat on the sublimation surface existing between the dry layer and the frozen layer. The water vapor generated on the sublimation surface condenses on the cold trap surface provided in the processing apparatus through the dry layer on the surface. In this process, drying of residual moisture proceeds in the dry layer, the frozen layer disappears, and the freeze-drying process ends. This process is characterized in that most of the free water is removed by sublimation, so that the process can proceed without being deformed or damaged by the sample.
As described above, in the vacuum freeze drying, a sample frozen in advance is placed on a drying shelf in a drying chamber, the drying chamber is evacuated, the ice in the sample is sublimated, and moisture is removed. The latent heat of sublimation necessary for evaporation in this case is supplied by the adjusted shelf temperature, and the larger the difference between the shelf temperature and the frozen layer (sample) temperature, the easier it is to dry. From the above, in the case of the general flow evaporation method of the fluid liquid by hot air drying, the shape and the component composition are affected and changed due to the mass transfer by the fluid. On the other hand, since most free water can be removed by sublimation in vacuum freeze-drying, mass transfer in the sample is greatly suppressed, and the sample is dried by protecting it from deformation and damage. It is a feature.
In the vacuum freeze-drying apparatus, a sample that is frozen at −10 ° C. or less obtained in the freezing step is placed on a vacuum freeze-drying chamber shelf that can adjust the degree of sublimation by temperature change, and the triple point or less. The sample is sublimated under the temperature and pressure conditions to sublimate ice to remove moisture. The shelf temperature can be set to a different temperature in order to investigate the effects of changes in the shelf temperature of the vacuum freeze-drying chamber. When an appropriate temperature is already known as the shelf temperature, there is no problem in performing the freeze-drying process at the shelf temperature.
Specifically, the sample is placed on a shelf maintained at 0 ° C., −20 ° C., −30 ° C., and −40 ° C. for processing.
In the case of a shelf of −40 ° C., it was found that the drying operation takes about 70% of the constant dryness by taking 3 to 4 hours. This corresponds to the processing of 24 to 48 hours required in the case of a drying process at 110 ° C., which means that the measurement time can be shortened.
The temperature of each sample dropped immediately after drying in the case of the set shelf temperature, and at the time of maximum sublimation, the maximum cooling temperature was −13 ° C. at −20 ° C., −17 ° C. at −30 ° C., and −16 at −40 ° C. The temperature gradually increased until the end of drying as it was, and constant cooling temperatures of −7 ° C., −7 ° C., and −10 ° C. were reached.
The decreasing rate of the sample temperature was different in the order of the set shelf temperature −20 ° C.> − 30 ° C.> − 40 ° C. This indicates the characteristics of the FD method in which the difference between the cold trap chamber temperature and the conduction heat from the shelf increases as the difference increases and the drying property is effective.
The mass reduction ratio of the fine-grained sample after drying for 24 hours showed 0.92 at a set shelf temperature of −20 ° C., −0.95 at −30 ° C. and −40 ° C. A shelf temperature of -20 ° C is a good result.
This vacuum freeze-drying apparatus is as follows.
The vacuum freeze-drying equipment consists of a drying chamber where the hardened cement specimen is frozen in the previous process, a cryogenic cold trap surface that condenses and collects the removed moisture generated in the drying chamber, and the subsequent outlet and drying. It consists of a high vacuum pump that keeps the room in a high vacuum.
The temperature and pressure conditions in the apparatus must be set at a temperature and pressure below the triple point (temperature 273.15 K (0 ° C.), pressure 633.3 Pa (4.6 Torr)).
There is a drying shelf that can adjust the temperature of the shelf by changing the temperature. Place the hardened cement specimen on the shelf.
By installing the freezing apparatus and the vacuum freeze-drying apparatus in the same tank, the freezing process and the vacuum freeze-drying process can be performed in the same tank.
When performing a freezing process, it operates so that the gas cooled so that the temperature which reaction stops substantially may be -10 degrees C or less is sent. In this case, the pressure pump is not operated. The shelf on which the sample is placed is set to the same temperature as the gas for cooling. The cooling time is determined by calculating the amount fed from the amount of gas required for cooling. When the freezing process is completed, the processing conditions are changed to the vacuum freeze-drying process. Specifically, the high vacuum pump is operated, the pressure is 3 Pa or less, usually 1 Pa or less, the temperature is 0 ° C. or less, the trap temperature is set to about −80 ° C. to −90 ° C., and the shelf temperature is from 0 ° C. It can set to about -20 degreeC which is between -40 degreeC.
In the embodiment of the present invention, the case where the freezing apparatus and the vacuum freeze-drying apparatus are performed separately has been described, but the specific case where the individual apparatuses are combined in the same tank from the case where these individual apparatuses are used is described. An example can be fully understood (FIG. 14). In this figure, in the upper left part, there is a freezing device that freezes the contained water, and a vacuum freeze-drying device that does not contain moisture by vacuum freeze-drying the sample in which the moisture is frozen in the same tank. It is shown as a device in the assembled state. A drying shelf is installed in one stage in the center. Below that, an annular cold trap is installed. A temperature control means is installed in the upper right of the apparatus. This can be switched according to the conditions of the two devices. In the lower part, equipment such as a vacuum pump for vacuum freeze-drying is arranged. The pressure adjusting means is also switched by the operation panel.
Regarding the sample for measurement of the invention, the sample containing water taken out as the sample for measurement was rapidly cooled below the temperature at which the reaction substantially stopped, the contained water was frozen, and the water was subsequently frozen. A sample obtained by lyophilizing a sample in a vacuum to remove moisture, or a sample containing moisture taken out as a measurement sample is a hardened cement, and the temperature at which the reaction substantially stops is − A measurement sample having a temperature of 10 ° C. or lower can be obtained.
The sample is placed under conditions kept at a low temperature and in a vacuum state. When used as a sample, the sample is used at normal temperature and pressure. Considering the use of a sample at room temperature and normal pressure, a process in which a sample kept in a vacuum at a low temperature is brought to a normal temperature and normal pressure state without changing the physical and chemical state of the sample. If done, the condition before using the sample is perfect.
The treatment for this is performed by heating the sample while filling it in the presence of an inert gas so that the sample is used at room temperature and normal pressure. If the sample is taken out under normal temperature and pressure without performing this operation, the surface of the sample may be changed by the atmosphere, and the surface of the sample may change.
The contents of the operation for heating the sample while filling it in the presence of an inert gas are as follows.
As the inert gas, an inert gas such as nitrogen, argon, neon, or helium can be used. Air (ratio of nitrogen 4 to oxygen 1) can also be used. When air is used, a process such as complete removal of moisture contained in the air is required. In order to remove moisture, a process of bringing air into contact with an adsorbent is performed. An inert gas or the like is supplied to the sample in the vacuum drying chamber. Then, the supply of the inert gas is continued, and the drying chamber in which the sample is placed is brought to a normal pressure state. In this case, the inert gas has a time of about 1 to 5 minutes, preferably about 2 to 3 minutes. Less than 1 minute is not preferable because it causes a rapid change in the sample. If it exceeds 5 minutes, it takes time unnecessarily, which is not preferable in preparing a sample.
After vacuum freeze-drying, the sample is at a temperature of -15 ° C or lower, -20 ° C or lower, under vacuum. When the sample is taken out from the freeze dryer and used, it is heated at about + 20 ° C., which is the same level as the outside air, in the freeze dryer because it is at the same room temperature as the outside air. Heating is performed using a heating means such as a heater. The heating time can be appropriately set, but is generally about 8 to 12 hours, preferably about 9 to 10 hours. When it is less than 8 hours, heating is abrupt, which is not preferable. Moreover, when it exceeds 12 hours, it takes time unnecessarily, and it is not appropriate for preparing a sample.
By setting a sample in a low temperature and vacuum state to normal temperature and pressure, if the sample is taken out immediately after lyophilization, it is possible to prevent condensation on the surface of the sample. Can prevent physical and chemical changes.
The sample preparation process is to complete the sample through a sample freezing step and a sample vacuum freeze-drying step, and then consider taking out the sample at a low temperature / vacuum state at room temperature / normal temperature. The sample to which pressure is applied is taken out.
On the other hand, the sample preparation process can be performed in a vacuum freeze-drying machine as a series of processes, including a sample freezing process, a sample vacuum freeze-drying process, and a process for returning to a normal temperature / normal pressure environment. According to this, since the sample can be manufactured as a series of steps, it is convenient when preparing the sample.
A method for preparing a sample as a series of steps including a sample freezing step, a sample vacuum freeze-drying step, and a step of returning to a normal temperature / normal pressure environment is as follows. The entire process is shown in FIG.
A sample piece (usually 2.50 to 5.00 mm) obtained by fine grain cutting is placed in a vacuum freeze dryer (in the vacuum freeze dryer, the sample freezing step, the sample vacuum freeze drying step, and then at room temperature) -Perform the process of returning to the normal pressure environment).
(1) Freezing step The sample at room temperature is set to about −30 ° C. by setting the shelf temperature to about −20 to −30 ° C. If the shelf temperature is −10 ° C. or lower, the sample can be frozen and the hydration reaction can be stopped. Freezing must be done rapidly. If the sample is a solid and the inside is to be cooled to the same temperature as the outside, a certain amount of time is required. Time needs to fully consider these phenomena. The time may be about 7 to 8 minutes, and the maximum time may be about 4 hours.
(2) Vacuum freeze-drying process In the vacuum freeze-drying apparatus, the sample which is the sample placed on the vacuum freeze-drying chamber shelf frozen at −10 ° C. or less obtained in the freezing process is subjected to a vacuum freeze-drying process. . Specifically, the shelf set temperature is set to about -15 ° C to -20 ° C. Naturally, the sample can be placed on a shelf maintained at −20 ° C., −30 ° C., and −40 ° C. for processing.
When the shelf temperature is set to exceed −20 ° C. in the range of −20 to −30 ° C. due to the freezing process, the temperature of the sample rises and exceeds −20 ° C., and −20 When the sample reaches a temperature exceeding ℃, it can be considered that the vacuum freeze-drying process is completed. Moreover, even if it is in the state exceeding -20 degreeC, drying of a sample can also advance by maintaining the state. Because of this, it can be completed in about 6 hours at the shortest. In order to increase the accuracy of measurement, the drying time can usually be about 20 to 48 hours.
(3) Step of returning to a normal temperature / normal pressure environment After vacuum freeze-drying, the sample is at a temperature of −15 ° C. or lower, about −20 ° C. or lower. It is in a vacuum environment. This is transferred to a normal temperature / normal pressure environment. An inert gas or the like is supplied to the sample in the lyophilization chamber in a vacuum state for about 2 to 3 minutes. As the inert gas, an inert gas such as nitrogen, argon, neon, or helium can be used. Air (ratio of nitrogen 4 to oxygen 1) can also be used. When air is used, a process such as complete removal of moisture contained in the air is required. In order to remove moisture, a process of bringing air into contact with an adsorbent is performed. After vacuum freeze-drying, the sample is at a temperature of about −20 ° C. or lower. When used as a sample, it is heated at about + 20 ° C. because it is at room temperature. For the heating, heating means such as a heater provided on the shelf of the freeze dryer is used. Although this heating time can be set as appropriate, it is generally performed over a period of about 8 to 12 hours. Although it is intended to change gently, it does not necessarily have to be gentle, and it can be rounded up or finished in a relatively short time. This process can prevent condensation on the surface of the sample when the sample is taken out immediately after lyophilization by placing the sample in a low temperature and vacuum state at normal temperature and pressure. It is possible to prevent physical and chemical changes of the sample due to condensation.
The series of processing steps varies depending on the material constituting the sample. Considering the fact that it varies depending on the sample, the time required as a whole may be finished in 6 to 7 hours in some cases.
With respect to the measurement sample of the present invention, the sample containing moisture taken out as the measurement sample is rapidly cooled to a temperature substantially lower than the reaction stop temperature, the contained moisture is frozen, and the moisture is subsequently frozen. A sample obtained by lyophilizing a sample in a vacuum state and removing moisture, or a sample containing moisture taken out as a measurement sample is a hardened cement and has a temperature at which the reaction substantially stops. Using a measurement sample having a temperature of −10 ° C. or less, it can be connected to a mercury intrusion porosimeter with a pressure measurement range of 0 to 30000 Psia, and pore measurement can be performed.
With respect to the measurement sample of the present invention, the sample containing water taken out as a measurement sample is rapidly cooled to a temperature substantially lower than the reaction stop temperature, the contained water is frozen, and the water is subsequently frozen. The samples obtained by removing the moisture by vacuum freeze-drying and the samples containing moisture taken out as measurement samples are hardened cement and have a temperature at which the reaction substantially stops. The sample was cooled to -10 ° C or lower, the contained water was frozen, and the sample obtained by removing the moisture by vacuum freeze-drying the sample in which the moisture was subsequently frozen was used. Structure, pore shape and distribution can be measured.
The measurement sample obtained by the present invention has a state and structure of the sample that accurately reflects the progress of the reaction occurring in the sample at a specific point in time as compared with the conventional measurement sample. Can be measured. Is.
The above-described measurement can be performed using the following known measurement method.
1. Spectral analysis method Infrared spectroscopy method etc. 2. X-ray analysis method X-ray fluorescence analysis method, etc. Structural analysis method Scanning electron microscope, mercury intrusion method (using the above-mentioned mercury intrusion porosimeter), gas adsorption method, X-ray CT method, etc. 4. Surface analysis method, transmission electron microscope, etc. Thermal analysis method Differential thermal analysis method, etc. Separation analysis method Gas chromatography etc. Elemental analysis method EPMA method, etc. Further, the measurement sample of the present invention is a device used in the measurement method, a spectroscopic analysis device, an X-ray analysis device, a structural analysis device, a surface analysis device, a thermal analysis device, a separation analysis device. The measurement can be carried out by attaching it as a measurement sample to the elemental analyzer and the EPMA apparatus.

（３）常温・常圧の環境に戻す工程
真空凍結乾燥機の棚上に低温・真空の環境のもとにおかれている試料を、不活性ガスを１分から５分程度、好ましくは２〜３分程度の時間で供給する。不活性ガスには、窒素、アルゴン、ネオン、ヘリウムなどの不活性ガスや空気（窒素４対酸素１の割合）を用いる。
真空凍結乾燥後に試料は、−２０℃程度又はそれ以下の温度の状態にある。試料として使用する場合は、常温であるから＋２０℃で程度に加熱する。加熱には、凍結乾燥機の棚の温度を１０〜３０℃に設定する。加熱時間は、８〜１２時間、好ましくは、９〜１０時間程度である。
（４）細孔測定装置
圧力測定範囲０〜３００００ＰＳｉの水銀圧入式ポロシメーターである。
実施例４
ＦＤ法
（１）ＦＤ法及びＤＤ法の手順
ＦＤ法の手順は、予め凍結した試料を真空凍結乾燥機により乾燥するものである。
また、比較として用いた従来のＤＤ法の手順も示した（図２）。
実施例５
（１）凍結温度と凍結降温性状との関係について
セメントの水和が実際的に停止する−１０℃以下の凍結温度（−１０℃、−２０℃、−３０℃、−４０℃）と試料の降温性状について実験し、検討を行った。
結果は、図３に示す。水和反応の停止する−１０℃までの降温時間は、凍結温度−２０℃以下で約７〜８分以下と、水和反応の進行の影響を実際的に無視できる極く短時間で、到達することが認められた。また、−２０℃への到達時間は、約４０分〜５分であった。
実施例６
（２）凍結温度が水和の進行に及ぼす影響
凍結温度と水和反応の進行の関係を−１５℃、−２０℃及び３０℃で、２４時間凍結した試料の細孔測定結果により、乾燥前の凍結温度の検討を行った。用いた細粒試料は、材齢１日、３日及び７日のＪＩＳモルタルである。
また、比較のためＤＤ法におけるアセトン浸漬時間（２４ｈ、４８ｈ、７２ｈ）が、水和の進行におよぼす影響の確認についても実験検討した。各材齢の試料の凍結温度と細孔量の関係は、表２に示す通りであって、各材齢の−２０℃及び３０℃の両者の細孔量は同等となることに対し、−１５℃の場合は、−２０℃及び３０℃の細孔量の約０．８５〜０．９５と減少した。このことは、水和は−１０℃で実際的に停止すると言われているが、−１２℃においてもわずかな水和の進行により、圧縮強度が増加する既往の報告と同様のことと考える。以上のことは、凍結温度を−２０℃以下とする必要があることを示すものである。この結果に比して、アセトンに２４ｈ、４８ｈ及び７２ｈ浸漬したＤＤ法の試料の細孔量は、ＦＤ法に比して約０．７７〜０．９１と全試料とも減少し、アセトン浸漬中の水和の進行が認められた。以上のことは、ＦＤ法の優位性を示すものである。

実施例７
乾燥室棚温度と乾燥性状との関係について
乾燥度は、前記したように棚温度と密接に関係するのでＦＤ法による細粒試料の乾燥性を実験検討した。
結果は図４の通りである。棚温度が高く、試料形状が小さいほど乾燥性は良好で、棚温度を４０℃とした場合、細孔測定に用いる細粒の乾燥度は、約３〜４時間と極く短時間で、図５に示す様に定乾燥度の約７０％となり、水和の進行の影響をほとんど受けずに乾燥できることが認められた。
実施例８
ＦＤ法による細粒試料の乾燥性について
ＦＤ法の乾燥性をＤＤ法の場合と比較検討した。
結果は、図５に示す通りである。ＦＤ法の乾燥性は、乾燥２４〜４８時間で定乾燥となり、ＤＤ法の４８〜７２時間より短時間で、より高乾燥となることが認められた。また図５に示す通りである。ＦＤ法の乾燥性は、乾燥２４〜４８時間で定乾燥となり、ＤＤ法の４８〜７２時間より短時間で、より高乾燥となることが認められた。
また図５には参考のため、アセトン浸漬を行っていない、２０℃−ＲＨ６５％、４５℃−ＲＨ３５％及び１１０℃で定質量となるまで乾燥した結果も示した。
実施例９
細粒試料の凍結保存性について
凍結温度を−３０℃とし、１日、３日及び９０日間凍結保存後、ＦＤ法を行った試料の細孔測定により、凍結保存性を検討した。細孔量の測定結果及び圧縮強度を表３に示す。この結果によれば、保存が９０日と長期であっても、凍結期間１日の細孔量と同等で、長期の凍結保存性が認められた。また、この長期凍結保存性は、圧縮強度でも同様に確認した。

実施例１０
ＦＤ法のセメント硬化体へおよぼす影響について
（１）強熱減量による検討
ＦＤ法、ＤＤ法及び１１０℃乾燥法の試料の強熱減量の定量方法（ＪＩＳ Ｒ ５２０２）により、測定した水和物の結合水の変化によって、各乾燥法の水和物への影響を検討した。
結果は表４の通りであり、ＦＤ法の１１０℃及び６００℃の結合水量は、ＤＤ法と同等で差異は認められないが、高乾燥（１１０℃）の場合より多く、ＤＤ法と同様に、ＦＤ法の水和物への影響の抑制効果が認められた。

実施例１１
（２）低加速電圧像（ＳＥＭ法）による検討
細粒試料表面を低加速電圧像の撮影が可能な小型走査型電子顕微鏡により、倍率２００倍で観察した。
測定試料は、ＦＤ法、ＤＤ法及び２０℃及び１１０℃の乾燥によりそれぞれ作成したものである。
測定写真を図６に示す。これらの結果によれば、ＦＤ乾燥の試料表面は、ＤＤ法及び２０℃乾燥の場合と同様に平滑で、差異は認められた。
実施例１２
ＦＤ法の細孔測定値に関する検討について
ＦＤ法により作成した試料の細孔測定値の信頼性を、材齢及びセメント水比及び各種セメントと細孔特性の関係、並びに測定値の変動について実験を行い、ＤＤ法（アセトン浸漬４８ｈ、乾燥７２ｈ）による場合と比較検討した。なお、ＤＤ法でアセトン浸漬時間を４８時間としたのは、図７のアセトン浸漬時間と試料の質量測定結果によるものである。以下に「３．１〜３．５」より定めたＦＤ法の各設定条件を示す。
イ．凍結温度及び時間：−３０℃、２４ｈ
ロ．乾燥室棚温度：４０℃
ハ．トラップ温度：−８５℃
ニ．真空度：１Ｐａ
ホ．試料：ＪＩＳモルタル細粒（２．５ｍｍ〜５．０ｍｍ）２．０ｇ
ヘ．乾燥時間：４８ｈ
（１） 材齢と細孔特性の関係について
材齢１日、３日、７日及び２８日と細孔量及び細孔径分布について実験検討した。
図８に細孔量の測定結果を示す。この結果によれば、ＦＤ法及びＤＤ法の場合とも、材齢の進行による細孔量は、材齢１日に対し、７日で０．６５〜０．７０及び２８日で約０．６と試料の作成方法に拘わらず同様に減少した。しかし、細孔量は試料作成方法により、相違することが認められた。すなわち、ＦＤ法の試料に比してＤＤ法の測定値は、０．８４〜０．９０と減少することが認められた。また、図９に、材齢１日及び３日の細孔径分布を示す様に、両材齢の場合ともＤＤ法の場合、大きな細孔が減少し、小さな細孔が増加していることも認められた。
以上のことはＤＤ法の場合、図５及び図７からも明らかな様に、アセトン置換中（４８ｈ）及び乾燥中（７２ｈ）の水和の進行によるものと言える。
実施例１３
（２） 水セメント比と細孔特性の関係について
ＦＤ法及びＤＤ法により、細孔量と水セメント比（０．４５、０．５０、０．５５、０．６０）の関係を実験検討した。配合はＷ／Ｃ＝５０％及びＳ／Ｃ＝３．０のＪＩＳモルタルの水量を調節したものである。
図１０にセメント水比と細孔量の関係を示す。この結果によれば、ＤＤ法の場合は両者間を論ずる結果は得られなかったが、ＦＤ法の測定結果では、セメント水比の増加に伴い細孔量が減少し、組織が緻密化する傾向が確認され、圧縮強度とセメント水比が比例することを裏付ける結果が得られた。
実施例１４
（３）セメントの種類と細孔特性の関係について
普通ポルトランドＣ（ＮＰＣ）、早強ポルトランドＣ（ＨＰＣ）、高炉ＣＢ種（ＢＦＣＢ）、フライアッシュＣＣ種（ＦＣＣ）、エコＣ（ＥＣ）の図１０にセメント水比と細孔量図１０にセメント水比と細孔量について実験検討した。各試料の品質はＷ／Ｃ＝５０％及びＳ／Ｃ＝３．０のモルタルである。
測定結果を図１１に示す。この結果によればＤＤ法の場合、セメントの種類と細孔量を論ずる結果は得られなかった。これに対し、ＦＤ法の場合、セメントの特性を良く表す結果を示した。すなわち、ＮＰＣに対し、ＨＰＣ及びＢＦＣＢはセメントの粉末度、あるいはスラグ微粉末による緻密化により、細孔量が減少し、ＦＣＣは材齢が２８日である。
測定結果を図１１に示す。この結果によれば、ＤＤ法の場合、セメントの種類と細孔量を論ずる結果は得られなかった。これに対し、ＦＤ法の場合、セメントの特性を良く表す結果を示した。すなわち、ＮＰＣに対し、ＨＰＣ及びＢＦＣＢはセメントの粉末度、あるいはスラグ微粉末による緻密化により、細孔量が減少し、ＦＣＣは材齢が２８日と短いので十分なポゾラン反応となっていないこと及びＥＣはセメントの鉱物組成の特殊性により、細孔量が微増することからである。
実施例１５
（４）ＦＤ法の細孔測定値の変動及び測定時間について
材齢１日、３日、７日及び２８日の４群の測定値の変動について、ＪＩＳモルタルにより実験検討した。結果は表５に示す通りであって、ＦＤ法の変動係数は、約１．０〜３．０％と安定しており、ＤＤ法の約３．０〜９．０％に比して高い信頼度を示した。次にＦＤ法による測定時間は、水銀圧入直前の脱気時間が約５分程度とＤＤ法（約２０分）の約１／４に短縮できることが認められた。

実施例１６
本実施例から得られる結果に基づく主な結論は、以下の通りである。
１）凍結温度−３０℃における、細粒試料の−１０℃への降温時間は約７〜８分で、実際的に水和の影響を受けない極く短時間で到達する。
２）ＦＤ法の試料による、材齢、セメント水比及びセメントの種類と細孔量の関係は、一般的に論じられている圧縮強度との関係を示す、良い指標となることが明確に認められた。
３）−３０℃で凍結した場合、凍結保存期間１日〜９０日の細孔測定値は同等で、試料の長期凍結保存性が認められた。
４）ＦＤ法試料の細孔量測定値の変動係数は、約１．０〜３．０％の範囲とＤＤ法（３．０〜９．０％）に比して安定しており、高い信頼性が認められた。
５）ポロシメーターの脱気時間は、ＦＤ法で約５分程度とＤＤ法（約２０分）の１／４と短く、測定時間の短縮が認められた。
実施例１７
試料の作成を、試料の凍結工程、試料の真空凍結乾燥工程、次に常温・常圧の環境に戻す工程を一連の工程として行った結果は以下の通りである。
細粒カットして得た試料片（２．００〜５．００ｍｍ）を、真空凍結乾燥機内に設置した（凍結工程、真空凍結乾燥工程、常温・常圧の環境に戻す工程を、真空凍結乾燥機内で行う。）。
真空凍結乾燥機内には、試料片を置く棚が設けられており、棚は複数段設置することができる。この棚の設定温度を調節することにより、冷却温度の設定、真空凍結乾燥温度の設定、常温・常圧の環境に戻す工程のための加熱温度の設定ができる。）。
試料の凍結工程、試料の真空凍結乾燥工程、次に常温・常圧の環境に戻す工程を、棚表面温度、真空凍結乾燥室温度（棚上１００ｍｍ）、試料中心温度（１０ｍｍ立方体）の温度変化と時間の関係として図１６に示した。
（１）凍結工程
凍結温度は−１０℃以下を規定するが、その温度は−１０℃以下であればよく、本実施例では棚設定温度を−３０℃とした。
４時間かけて凍結工程を終了した。
（２）真空凍結乾燥工程
棚の設定温度を−２０℃で処理して試料を、乾燥時間は２０時間であった。棚の表面温度は−２０℃に設定した。試料は２時間をかけて−２０℃を超え、以後、僅かづつ上昇し−１５℃程度で推移した。棚の表面温度は４時間を経過したところで試料の温度よりやや低下した。
真空凍結乾燥装置内の温度は棚上１００ｍｍのところで、−１２℃程度で僅かに上昇傾向にあった。
（３）常温・常圧の環境に戻す工程については、真空凍結乾燥装置内の棚の温度を３０℃として１６時間処理した。使用した不活性ガスは窒素ガスを３分間供給した。
試料の凍結工程、試料の真空凍結乾燥工程、次に常温・常圧の環境に戻す工程を、棚表面温度、真空凍結乾燥室温度（棚上１００ｍｍ）、試料中心温度（１０ｍｍ立方体）の温度変化と時間の関係として図１６に示した。
実施例１８
試料（ＳＪ（スーパージェットセメント）によるセメント・ペースト（ＣＰ）。水／セメント（Ｗ／Ｃ）比＝５０％。材齢３時間（ｈ））について、各乾燥の種類及び乾燥時間を変化させたときの強度の変化を測定した。
結果を図１７に示した。ＦＤ法による場合には乾燥時間によっては、強度はほぼ一定に保たれ、低下しない状態を示している（ＦＤ−４ｈにつき１−２（時間経過）。ＦＤ−６ｈにつき１−２（時間経過））。
ＤＤ法による場合には乾燥時間が経過すると、強度は低下することを示している。
（ＤＤ−７ｄにつき１−２（時間経過）。ＤＤ−１４につき１−２（時間経過）。ＤＤ−２１ｄにつき１−２（時間経過）。ＤＤ−２８ｄにつき１−２（時間経過））。
図１７におけるＦＤ−４ｈは、ＮＦＤ（ＦＤ法）４ｈとしてＳＡＭＥの観察結果を図１８〜２０に示す（図１７：ＮＦＤ−４ｈ−▲１▼、図１８：ＮＦＤ−４ｈ−▲２▼、図１９：ＮＦＤ−４ｈ−▲３▼。以上３点についての測定結果。）
各図では最上部のものが５，０００倍、中間部のものが１０，０００、最下部のものが１５，０００倍である。
各試料につきＳＡＭＥの結果を示す。スーパージェットセメントによるユトリンガイドの針状結晶を示している。結晶が明確に観察することができる。
図１７におけるＦＤ−６ｈは、ＮＦＤ（ＦＤ法）６ｈとしてＳＡＭＥの観察結果を図２１〜２３に示す（図２１：ＮＦＤ−６ｈ−▲１▼、図２２：ＮＦＤ−６ｈ−▲２▼、図２３：ＮＦＤ−６ｈ−▲３▼。以上３点についての測定結果。）
各図では最上部のものが５，０００倍、中間部のものが１０，０００、最下部のものが１５，０００倍である
各試料につきＳＡＭＥの結果を示す。スーパージェットセメントによるユトリンガイドの針状結晶を示している。結晶が明確に観察することができる。
図１７におけるＤＤ−７ｄのＳＡＭＥの観察結果を図２４〜２６に示す（図２４：ＤＤ−７−ｄ▲１▼、図２５：ＤＤ−７−ｄ▲２▼、図２６ＤＤ−７−ｄ▲３▼。以上３点についての測定結果。）
各図では最上部のものが５，０００倍、中間部のものが１０，０００、最下部のものが１５，０００倍である。
図１７におけるＤＤ１４ｄのＳＡＭＥの観察結果を図２７〜２９に示す（図２７：ＤＤ−１４−ｄ▲１▼、図２８：ＤＤ−１４−ｄ▲２▼、図２９：ＤＤ−１４−ｄ▲３▼。以上３点についての測定結果。）
各々の図は最上部のものが５，０００倍、中間部のものが１０，０００、最下部のものが１５，０００倍である。
図１７におけるＤＤ２１ｄのＳＡＭＥの観察結果を図３０〜３２に示す（図３０：ＤＤ−２１−ｄ▲１▼、図３１：ＤＤ−２１−ｄ▲２▼、図３２：ＤＤ−２１−ｄ▲３▼。以上３点についての測定結果。）
各々の図は最上部のものが５，０００倍、中間部のものが１０，０００、最下部のものが１５，０００倍である。
図１７におけるＤＤ２８ｄのＳＡＭＥの観察結果を図３３〜３５に示す（図３３：ＤＤ−２８−ｄ▲１▼、図３４：ＤＤ−２８−ｄ▲２▼、図３５：ＤＤ−２８−ｄ▲３▼。以上３点についての測定結果。）
各々の図は最上部のものが５，０００倍、中間部のものが１０，０００、最下部のものが１５，０００倍である。
以上の測定結果を観察すると、ＮＦＤ（ＦＤ法）の場合には表面構造は、４ｈ、６ｈを対比してみれば明らかがであるが、鮮明な状態を保っていることがわかる。一方、ＤＤ法では７ｄ、１４ｄ、２１ｄ、２８ｄと比較すると、徐々に不鮮明となっていくことがわかる。
この結果からＮＦＤ（ＤＤ）法では良好な状態を保っていることがわかる。The contents of the present invention will be described below with reference to examples. The present invention is not limited to this.
Example 1
Materials used and blending of mortar Cement is normal Portland cement (density: 3.16 g / cm ³ , specific surface area: 3260 cm ² / g), and fine aggregate is JIS R 5201, particle size of 2 mm used in the physical test of cement The following ISO standard sand (density 2.64 g / cm ³ , water absorption: 0.42%) was used. The blend of mortar used in the experiment is a standard mortar (JIS mortar) having a blend of W / C = 0.5 and S / C = 3.0.
Example 2
Preparation of samples used in each experiment (1) For pore measurement Samples are generally used fine particles of 2.5 mm to 5 mm. This fine-grained sample is obtained by cutting a 40 × 40 × 160 mm specimen after predetermined curing in water, cutting the vicinity of the center with a cutter in consideration of cracking due to crushing. Moreover, the amount of pore samples used for one pore measurement corresponded to a sample container (cell) used for a mercury intrusion porosimeter, and was about 2.0 g (about 10 fine particles).
(2) Freezing and cooling properties for examination The sample is the above-mentioned JIS mortar of 28 days of age, and the center of the disk having a diameter of 12 mm and a thickness of 10 mm is prepared in consideration of the pore measurement sample size described in (1) above. A thermocouple (CC) is embedded.
(3) Drying chamber shelf temperature and sample drying properties for examination 28-year-old JIS mortar, fine-grained sample, 40 × 40 × 10 mm flat plate and 40 × 40 × 160 mm prism There are three types.
Example 3
Equipment to be used (1) Freezing device + It is a constant temperature and humidity machine with an internal capacity of 408 L (liter) having a temperature drop performance within 60 minutes from 20 ° C. to −40 ° C.
(2) Vacuum freeze dryer A vacuum freeze dryer with a dehumidifying performance of 10 L whose specifications are shown in Table 1 is shown.
FIG. 1 shows a vacuum freeze dryer. The vacuum freeze dryer is composed of a drying chamber having a drying shelf with a temperature control function, a cryogenic cold trap chamber for condensing and collecting removed moisture on the cold trap surface, and a high vacuum pump.

(3) Step of returning to a normal temperature / normal pressure environment A sample placed on a shelf of a vacuum freeze dryer under a low temperature / vacuum environment is treated with an inert gas for 1 to 5 minutes, preferably 2 to 2 minutes. Supply in about 3 minutes. As the inert gas, an inert gas such as nitrogen, argon, neon, or helium or air (ratio of nitrogen 4 to oxygen 1) is used.
After vacuum freeze-drying, the sample is at a temperature of about −20 ° C. or lower. When used as a sample, it is heated at about + 20 ° C. because it is at room temperature. For heating, the temperature of the shelf of the freeze dryer is set to 10 to 30 ° C. The heating time is 8 to 12 hours, preferably about 9 to 10 hours.
(4) Pore measuring device A mercury intrusion porosimeter with a pressure measurement range of 0 to 30000PSi.
Example 4
FD Method (1) Procedure of FD Method and DD Method The procedure of the FD method is to dry a previously frozen sample with a vacuum freeze dryer.
Moreover, the procedure of the conventional DD method used as a comparison is also shown (FIG. 2).
Example 5
(1) Relationship between freezing temperature and freezing and cooling properties Cement hydration actually stops Freezing temperatures below -10 ° C (-10 ° C, -20 ° C, -30 ° C, -40 ° C) and the sample Experiments and examinations were conducted on the temperature drop characteristics.
The results are shown in FIG. The temperature lowering time to -10 ° C when the hydration reaction is stopped is about 7-8 minutes or less at a freezing temperature of -20 ° C or less. Admitted to do. Moreover, the time to reach −20 ° C. was about 40 minutes to 5 minutes.
Example 6
(2) Effect of freezing temperature on the progress of hydration The relationship between the freezing temperature and the progress of the hydration reaction was determined by the pore measurement results of the samples frozen at −15 ° C., −20 ° C. and 30 ° C. for 24 hours before drying. The freezing temperature of was examined. The fine-grained sample used was JIS mortar with a material age of 1, 3, and 7 days.
For comparison, an experiment was also conducted to confirm the effect of the acetone immersion time (24 h, 48 h, 72 h) in the DD method on the progress of hydration. The relationship between the freezing temperature and the amount of pores of the samples of each age is as shown in Table 2, and both the −20 ° C. and 30 ° C. pores of each age are equivalent, In the case of 15 ° C., the amount of pores at −20 ° C. and 30 ° C. decreased to about 0.85 to 0.95. Although it is said that hydration actually stops at -10 ° C, this is considered to be the same as the previous report that the compressive strength increases due to slight progress of hydration at -12 ° C. The above shows that the freezing temperature needs to be −20 ° C. or lower. Compared with this result, the pore volume of the DD method samples immersed in acetone for 24 h, 48 h, and 72 h was about 0.77 to 0.91 compared to the FD method, and all the samples were reduced. Progression of hydration was observed. The above shows the superiority of the FD method.

Example 7
Relationship between drying chamber shelf temperature and drying properties Since the drying degree is closely related to the shelf temperature as described above, the drying property of the fine-grained sample by the FD method was experimentally examined.
The result is as shown in FIG. The higher the shelf temperature and the smaller the sample shape, the better the drying property. When the shelf temperature is 40 ° C., the dryness of the fine granules used for pore measurement is about 3 to 4 hours, As shown in FIG. 5, it became about 70% of the constant dryness, and it was confirmed that the film could be dried with almost no influence of the progress of hydration.
Example 8
About the drying property of the fine grain sample by FD method The drying property of FD method was compared with the case of DD method.
The results are as shown in FIG. It was confirmed that the drying property of the FD method became constant drying in 24 to 48 hours of drying, and higher drying in a shorter time than 48 to 72 hours of the DD method. Also as shown in FIG. It was confirmed that the drying property of the FD method became constant drying in 24 to 48 hours of drying, and higher drying in a shorter time than 48 to 72 hours of the DD method.
For reference, FIG. 5 also shows the results of drying to constant mass at 20 ° C.-RH 65%, 45 ° C.-RH 35%, and 110 ° C. without acetone immersion.
Example 9
Cryopreservability of the fine-grained sample The cryopreservation property was examined by measuring the pores of samples subjected to the FD method after freezing at a freezing temperature of −30 ° C. for 1, 3, and 90 days. Table 3 shows the measurement results of the pore amount and the compressive strength. According to this result, even if the storage was as long as 90 days, the long-term cryopreservability was recognized as being equivalent to the amount of pores during the freezing period of 1 day. This long-term cryopreservation property was also confirmed in the compressive strength.

Example 10
Effect of FD method on hardened cement (1) Examination by ignition loss of hydrate measured by quantification method (JIS R 5202) of ignition loss of sample of FD method, DD method and 110 ° C drying method The effect of each drying method on hydrates was examined by the change in bound water.
The results are as shown in Table 4. The amount of bound water at 110 ° C. and 600 ° C. in the FD method is the same as that in the DD method and no difference is observed, but more than in the case of high drying (110 ° C.). In addition, an inhibitory effect on the influence of the FD method on the hydrate was observed.

Example 11
(2) Examination by Low Acceleration Voltage Image (SEM Method) The surface of a fine-grained sample was observed at a magnification of 200 times with a small scanning electron microscope capable of photographing a low acceleration voltage image.
The measurement samples were prepared by the FD method, the DD method, and drying at 20 ° C. and 110 ° C., respectively.
A measurement photograph is shown in FIG. According to these results, the sample surface of FD drying was smooth as in the case of the DD method and 20 ° C. drying, and a difference was observed.
Example 12
Study on pore measurement value of FD method Experiment on reliability of pore measurement value of sample prepared by FD method, age and cement water ratio, relationship between various cement and pore characteristics, and fluctuation of measurement value This was compared with the case of the DD method (acetone immersion 48 h, dry 72 h). The reason why the acetone immersion time was set to 48 hours in the DD method was based on the acetone immersion time in FIG. 7 and the mass measurement result of the sample. Each setting condition of the FD method defined from “3.1 to 3.5” is shown below.
I. Freezing temperature and time: -30 ° C, 24h
B. Drying room shelf temperature: 40 ° C
C. Trap temperature: -85 ° C
D. Degree of vacuum: 1Pa
E. Sample: JIS mortar fine granules (2.5 mm to 5.0 mm) 2.0 g
F. Drying time: 48h
(1) Relationship between material age and pore characteristics Experiments were conducted on the age, 1 day, 3 days, 7 days, and 28 days, the amount of pores and the pore size distribution.
FIG. 8 shows the measurement results of the amount of pores. According to this result, in both the FD method and the DD method, the amount of pores due to the progress of material age is 0.65 to 0.70 for 7 days and about 0.6 for 28 days with respect to 1 day of material age. It was similarly reduced regardless of the sample preparation method. However, it was recognized that the amount of pores differs depending on the sample preparation method. That is, it was recognized that the measured value of the DD method decreased from 0.84 to 0.90 as compared with the sample of the FD method. In addition, as shown in FIG. 9, the pore size distribution at the age of 1 day and 3 days, in the case of the DD method for both ages, large pores are decreased and small pores are increased. Admitted.
In the case of the DD method, the above can be said to be due to the progress of hydration during acetone substitution (48 h) and drying (72 h), as is apparent from FIGS. 5 and 7.
Example 13
(2) Relationship between water cement ratio and pore characteristics The relationship between pore volume and water cement ratio (0.45, 0.50, 0.55, 0.60) was experimentally examined by the FD method and DD method. . The composition is adjusted by adjusting the amount of water of JIS mortar with W / C = 50% and S / C = 3.0.
FIG. 10 shows the relationship between the cement water ratio and the amount of pores. According to this result, in the case of the DD method, the result of discussing between the two was not obtained, but in the measurement result of the FD method, the amount of pores decreased as the cement water ratio increased, and the structure tends to become denser. As a result, it was confirmed that the compressive strength and the cement water ratio are proportional.
Example 14
(3) Relationship between cement type and pore characteristics Normal Portland C (NPC), Hayao Portland C (HPC), Blast Furnace CB (BFFC), Fly Ash CC (FCC), Eco C (EC) Fig. 10 shows the cement water ratio and the amount of pores. Fig. 10 shows the cement water ratio and the amount of pores. The quality of each sample is mortar with W / C = 50% and S / C = 3.0.
The measurement results are shown in FIG. According to this result, in the case of the DD method, a result of discussing the kind of cement and the amount of pores was not obtained. On the other hand, in the case of the FD method, the result showing the characteristics of the cement well was shown. That is, with respect to NPC, HPC and BFCB have a reduced amount of pores due to cement fineness or densification with fine slag powder, and FCC has a material age of 28 days.
The measurement results are shown in FIG. According to this result, in the case of the DD method, a result of discussing the type of cement and the amount of pores was not obtained. On the other hand, in the case of the FD method, the result showing the characteristics of the cement well was shown. In other words, HPC and BFCB have a fine pozzolanic reaction due to the fineness of cement fineness or densification with slag fine powder, and FCC has a short age of 28 days compared to NPC. And EC is because the amount of pores slightly increases due to the peculiarity of the mineral composition of cement.
Example 15
(4) Fluctuation in pore measurement value and measurement time of FD method The fluctuation of the measurement value in the four groups of material ages 1, 3, 7, and 28 was experimentally examined by JIS mortar. The results are shown in Table 5. The coefficient of variation of the FD method is stable at about 1.0 to 3.0%, which is higher than that of the DD method of about 3.0 to 9.0%. The reliability was shown. Next, it was confirmed that the measurement time by the FD method can be shortened to about ¼ of the degassing time immediately before the mercury intrusion by about 5 minutes, which is about ¼ of the DD method (about 20 minutes).

Example 16
The main conclusions based on the results obtained from this example are as follows.
1) When the freezing temperature is −30 ° C., the temperature of the fine-grained sample to −10 ° C. is about 7 to 8 minutes, and it reaches in a very short time without being affected by hydration.
2) It is clearly recognized that the relationship between age, cement water ratio, cement type, and pore volume by the FD sample is a good indicator of the relationship with the compression strength generally discussed. It was.
3) When frozen at −30 ° C., the pore measurement values of the cryopreservation period of 1 day to 90 days were equivalent, and the long-term cryopreservation property of the sample was observed.
4) The coefficient of variation of the measured pore amount of the FD method sample is stable in comparison with the DD method (3.0 to 9.0%) in the range of about 1.0 to 3.0% and high. Reliability was recognized.
5) The degassing time of the porosimeter was about 5 minutes by the FD method and 1/4 of the DD method (about 20 minutes), and the measurement time was shortened.
Example 17
The results of performing the sample preparation as a series of steps including a sample freezing step, a sample vacuum freeze-drying step, and a step of returning to a normal temperature / normal pressure environment are as follows.
Sample pieces (2.00 to 5.00 mm) obtained by fine-grain cutting were placed in a vacuum freeze dryer (freezing process, vacuum freeze drying process, and process of returning to a normal temperature / normal pressure environment by vacuum freeze drying) On board).
In the vacuum freeze dryer, a shelf on which sample pieces are placed is provided, and a plurality of shelves can be installed. By adjusting the set temperature of the shelf, it is possible to set the cooling temperature, the vacuum freeze-drying temperature, and the heating temperature for the process of returning to the normal temperature / normal pressure environment. ).
Sample freezing step, sample vacuum lyophilization step, and then returning to normal temperature / normal pressure environment, shelf surface temperature, vacuum freeze drying chamber temperature (100 mm on shelf), sample center temperature (10 mm cube) temperature change FIG. 16 shows the relationship between time and time.
(1) Freezing step The freezing temperature is defined as −10 ° C. or lower, but the temperature may be −10 ° C. or lower, and the shelf set temperature is −30 ° C. in this example.
The freezing process was completed over 4 hours.
(2) Vacuum freeze-drying step The sample was processed at a shelf set temperature of -20 ° C, and the drying time was 20 hours. The surface temperature of the shelf was set to -20 ° C. The sample exceeded −20 ° C. over 2 hours, and then gradually increased and shifted to about −15 ° C. The shelf surface temperature dropped slightly from the sample temperature after 4 hours.
The temperature in the vacuum freeze-drying apparatus tended to increase slightly at about −12 ° C. at 100 mm on the shelf.
(3) About the process which returns to the environment of normal temperature and a normal pressure, the temperature of the shelf in a vacuum freeze-drying apparatus was processed at 16 degreeC for 16 hours. The inert gas used was nitrogen gas supplied for 3 minutes.
Sample freezing step, sample vacuum lyophilization step, and then returning to normal temperature / normal pressure environment, shelf surface temperature, vacuum freeze drying chamber temperature (100 mm on shelf), sample center temperature (10 mm cube) temperature change FIG. 16 shows the relationship between time and time.
Example 18
For each sample (cement paste (CP) by SJ (super jet cement), water / cement (W / C) ratio = 50%, age 3 hours (h)), each drying type and drying time were changed. The change in intensity was measured.
The results are shown in FIG. In the case of the FD method, the strength is maintained almost constant depending on the drying time, indicating that it does not decrease (1-2 for FD-4h (elapsed time), 1-2 for FD-6h (elapsed time)). ).
In the case of the DD method, the strength decreases as the drying time elapses.
(1-2 (time lapse) per DD-7d. 1-2 (time lapse) per DD-14. 1-2 (time lapse) per DD-21d. 1-2 (time lapse) per DD-28d).
FD-4h in FIG. 17 is an NFD (FD method) 4h, and SAME observation results are shown in FIGS. 18 to 20 (FIG. 17: NFD-4h- <1>, FIG. 18: NFD-4h- <2>, FIG. 19: NFD-4h- <3> Measurement results for the above three points.)
In each figure, the top one is 5,000 times, the middle one is 10,000, and the bottom one is 15,000 times.
The SAME results are shown for each sample. It shows needle-like crystals of utrine guide made of super jet cement. Crystals can be clearly observed.
FD-6h in FIG. 17 shows the observation results of SAME as NFD (FD method) 6h (FIG. 21: NFD-6h- <1>, FIG. 22: NFD-6h- <2>, FIG. 23: NFD-6h- <3> Measurement results for the above three points.)
In each figure, the top one is 5,000 times, the middle one is 10,000, and the bottom one is 15,000 times. The SAME results are shown for each sample. It shows needle-like crystals of utrine guide made of super jet cement. Crystals can be clearly observed.
The observation results of SAME of DD-7d in FIG. 17 are shown in FIGS. 24-26 (FIG. 24: DD-7-d 1), FIG. 25: DD-7-d 2 and FIG. 26DD-7-d 3 ▼ .Measurement results for the above three points.)
In each figure, the top one is 5,000 times, the middle one is 10,000, and the bottom one is 15,000 times.
The observation results of the SAME of DD14d in FIG. 17 are shown in FIGS. 27 to 29 (FIG. 27: DD-14-d (1), FIG. 28: DD-14-d (2), FIG. 29: DD-14-d) 3 ▼ .Measurement results for the above three points.)
In each figure, the top one is 5,000 times, the middle one is 10,000, and the bottom one is 15,000 times.
The observation results of the SAME of DD21d in FIG. 17 are shown in FIGS. 30 to 32 (FIG. 30: DD-21-d (1), FIG. 31: DD-21-d (2), FIG. 32: DD-21-d ▲). 3 ▼ .Measurement results for the above three points.)
In each figure, the top one is 5,000 times, the middle one is 10,000, and the bottom one is 15,000 times.
The observation results of the SAME of DD28d in FIG. 17 are shown in FIGS. 33 to 35 (FIG. 33: DD-28-d (1), FIG. 34: DD-28-d (2), FIG. 35: DD-28-d ▲). 3 ▼ .Measurement results for the above three points.)
In each figure, the top one is 5,000 times, the middle one is 10,000, and the bottom one is 15,000 times.
Observing the above measurement results, it can be seen that in the case of NFD (FD method), the surface structure is clear by comparing 4h and 6h, but is kept clear. On the other hand, it can be seen that the DD method is gradually blurred as compared with 7d, 14d, 21d, and 28d.
This result shows that the NFD (DD) method maintains a good state.

  In the case where it is necessary to stop the hydration reaction of the material and to investigate the progress of the hydration reaction, an effective means is provided.

Claims (20)

  Regarding samples for measurement, samples containing moisture taken out as samples, rapidly cooled below the temperature at which the reaction substantially stops, freezing the contained moisture, and subsequently in a state where the moisture is frozen A sample for measurement, which is obtained by lyophilizing and removing water.   2. The sample for measurement according to claim 1, wherein the sample containing moisture taken out as the sample for measurement is a cement hardened body, and the temperature at which the reaction substantially stops is −10 ° C. or lower.   A measurement sample obtained by heating the sample while filling the measurement sample according to claim 1 or 2 in the presence of an inert gas to bring it to a normal temperature and normal pressure state.   Concerning the measurement sample, the sample containing water taken out as the measurement sample is rapidly cooled to a temperature substantially lower than the reaction stop temperature, the contained water is frozen, and the moisture is subsequently frozen. The sample can be obtained by lyophilizing the sample to remove moisture, and heating the sample while filling with the inert gas in the presence of the resulting sample to bring it to room temperature and normal pressure. A measurement sample characterized by   The water-containing sample taken out as a measurement sample is a hardened cement, and the temperature at which the reaction substantially stops is −10 ° C. or lower, and the sample in which the water is subsequently frozen is −10 ° C. or lower. Obtained by removing the moisture by vacuum lyophilization under the above conditions, and heating the sample while filling it in the presence of an inert gas to bring it to a normal temperature and normal pressure state. The measurement sample according to claim 4, wherein the measurement sample is obtained.   Regarding the sample for measurement, the sample containing water taken out as the sample for measurement is rapidly cooled in the vacuum freeze dryer below the temperature at which the reaction substantially stops to freeze the contained water, and subsequently the water content The sample in a frozen state is lyophilized in vacuum to remove the moisture, and the sample from which the moisture has been removed is heated while continuing to be filled with an inert gas to obtain a normal temperature and normal pressure state. A measurement sample obtained by performing the process.   The sample containing moisture taken out as a measurement sample is a hardened cement, and the temperature at which the reaction substantially stops is −30 ° C. or less, and the sample in which moisture is subsequently frozen is −20 ° C. or less. Water was removed by lyophilization under vacuum conditions, and the sample from which the resulting moisture was removed was heated at 30 ° C. while being filled with an inert gas, and brought to a normal temperature and normal pressure state. The measurement sample according to claim 6, wherein the measurement sample is obtained.   Regarding a measurement sample manufacturing apparatus, a sample containing water taken out as a measurement sample is rapidly cooled below a temperature at which the reaction substantially stops to freeze the contained water, and the water is frozen. An apparatus for producing a sample for pore measurement, comprising: a vacuum freeze-drying apparatus that freeze-drys the sample in a dried state so as not to contain moisture.   9. The sample for pore measurement according to claim 8, wherein the sample containing moisture taken out as a measurement sample is a hardened cement, and the temperature at which the reaction substantially stops is −10 ° C. or less. Manufacturing equipment.   The apparatus for producing a sample for pore measurement according to claim 8 or 9, characterized in that an apparatus for heating the sample while being filled with an inert gas to bring it to a normal temperature and pressure state is installed. An apparatus for producing a sample for pore measurement.   Regarding a manufacturing apparatus for a sample for measuring pores, a freezing apparatus that rapidly cools a sample containing moisture taken out as a measurement sample to a temperature at which the reaction substantially stops and freezes the contained moisture, and subsequently Vacuum freezing equipment that removes moisture by vacuum freeze-drying the sample in a state where the moisture is frozen, and heating the sample while filling the obtained moisture-free sample in the presence of an inert gas, An apparatus for producing a sample for measuring pores, characterized in that the apparatus comprises   The sample containing water taken out as a measurement sample is a cement hardened body, and the temperature at which the reaction substantially stops is −10 ° C. or lower, and the sample in which the water is frozen is subsequently −10 A vacuum freezing device that removes moisture by vacuum freeze-drying under a temperature of ℃ or less, and the sample obtained by removing moisture is heated in the presence of an inert gas and filled with an inert gas at room temperature and normal pressure. (11) The apparatus for producing a sample for pore measurement according to (11).   Concerning production equipment for pore measurement samples, samples containing water taken out as measurement samples are rapidly cooled in a vacuum freeze dryer to a temperature that substantially stops the reaction, and the contained water is frozen. Freezing step, followed by vacuum freeze-drying the sample in which the moisture is frozen to remove the moisture, then the vacuum freezing step to remove the obtained moisture, and subsequently heating the sample while filling in the presence of inert gas An apparatus for producing a sample for measuring pores, characterized by performing a step of bringing the temperature to normal temperature and pressure.   A sample containing moisture taken out as a measurement sample is a hardened cement, and a freezing step in which the temperature at which the reaction substantially stops is −30 ° C. or lower, and subsequently a sample in which the moisture is frozen is −20. A vacuum freezing process in which the water is removed by lyophilization under vacuum at a temperature of ℃ or lower, followed by a process of heating the sample at 30 ℃ while filling it in the presence of an inert gas to bring it to room temperature and normal pressure. 14. The apparatus for producing a sample for pore measurement according to claim 13,   A pore measurement method, comprising performing pore measurement using the measurement sample according to claim 1.   The method for measuring pores according to claim 15, wherein the method for measuring pores is a mercury intrusion method.   A measurement apparatus according to any one of claims 1 to 7, wherein the measurement sample is used in a measurement apparatus.   18. The pore measuring device according to claim 17, wherein the pore measuring device is a mercury intrusion type pore measuring device.   The measurement sample according to any one of claims 1 to 7, wherein a spectroscopic analysis method, an X-ray analysis method, a structural analysis method, a surface analysis method, a thermal analysis method, a separation analysis method, an elemental analysis method, and an EPMA method are used. A measurement method characterized by being used in the method according to any one of the above.   The measurement sample according to any one of claims 1 to 7, wherein a spectroscopic analyzer, an X-ray analyzer, a structure analyzer, a surface analyzer, a thermal analyzer, a separation analyzer, an element analyzer, and an EPMA device are used. A measuring apparatus used for the apparatus according to any one of the above.

Images