JPS589853A - Manufacture of inorganic hardened body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to the Ojl method for producing inorganic cured materials used as building materials such as exterior wall materials.

Conventionally, fiber cement paperboards whose main component is relatively lightweight granulated blast furnace slag with a bulk specific gravity of around 1.00 or its warm cement have been generally manufactured by a papermaking method.

It is used as a building material, etc. However, this cement paper board had the drawbacks of low strength, poor flexibility, and relatively large dry shrinkage. To improve this drawback, calcium silicate was added.

The performance of cement paperboard was improved. As a result, 1 strength was strong and drying shrinkage 4 was small, but on the other hand,
When freezing damage resistance decreases and the papermaking method is used),
The filtration time of the slurry was long (due to poor aqueous properties), and furthermore, the pressure moldability was insufficient and clutter easily formed in the excipients. A paper-made board with aluminate monosulfate hydrate and gypsum added is also used, but this paper-made board has 4F water-based properties, 11a pressure moldability 9II green hardening speed, drying shrinkage, frost damage resistance 9 strength, etc. In terms of product physical properties, the product was sufficiently satisfactory and did not meet Fi.

This W14Fi was developed in consideration of these circumstances, and has high strength, low drying shrinkage, and excellent frost resistance.
Furthermore, the slag hardens quickly! 4, which provides a method for producing hIIA machine-cured products that exhibits a temperature of 111 degrees and shortens the production time from papermaking to agricultural products. This will be explained below.

There are two methods for producing the inorganic hardened body according to the present invention. The first method is to shape a slurry containing granulated blast furnace slag or its mixed cement, calcium silicate, gypsum, and reinforcing fibers, and then cure and harden it. This is a method for obtaining an inorganic cured product from Toto K.

The mixing ratio of granulated blast furnace slag or its mixed cement, calcium silicate, and gypsum.

The second method is characterized in that calcium silicate is 10% by weight or less, gypsum (as dihydrate gypsum) is 30% by weight or less, and the remainder is granulated slag or cement mixed therewith. After forming a slurry containing granulated blast furnace slag or its warm cement, calcium silicate, calcium alkinate monosulfate hydrate/gypsum, and reinforcing fibers, it is biocured to produce an inorganic hardened body. A method of obtaining granulated blast furnace slag or its mixed cement, calcium silicate, calcium aluminate monosal 7 ate hydrate, and gypsum in a blending ratio among the four components, 60-95 weight -, calcium silicate is 1 (
It is characterized in that the total amount of calcium 7 ium aluminate mononal 7 ate hydrate converted to dihydrate gypsum and added to gypsum (as dihydrate gypsum) is set at 30 weight lee below 1 weight. Jinre will be explained below in FK Details 111.

In this method, granulated blast furnace slag is used as an inorganic binder, but this granulated blast furnace slag may also be used in the form of a mixed cement with Portland cement or the like added thereto.

Therefore, the main component of the matrix is granulated blast furnace slag or its mixed cement. As calcium silicate#
For example, crystalline or amorphous hydrated calcium silicate, such as xonotlite, tobermorite, or calcium silicate, is used. This material is preferably used in the form of a calcium silicate slurry so that it can be easily mixed with other raw materials. For example, a hydrated calcium silicate slurry obtained by curing (previously heat curing) in an autoclave from silicic acid raw materials and lime raw materials may be used as an aqueous slurry without drying. .

Gypsum is crystalline gypsum (dihydrate).

Semi-permanent gypsum (#gypsum, hemihydrate salt, ): 'Anhydrous gypsum (anhydrous salt), etc.' Which is best to use.

In the first method, the mixing ratio of granulated blast furnace slag or its mixed cement, calcium silicate, and gypsum must be set as follows. That is, the amount of calcium silicate is 16 weight - (hereinafter abbreviated as "%") or less. It is most preferable that O, S be blended in a range of 896 or higher. Gypsum #i' is to be blended as dihydrogypsum at 30- or less. It is most preferable to mix in a range of IIG or more and 25 or less □ = and the blend of high granulated slag or its mixed cement is the remainder after excluding calcium silicate and gypsum.

Next, in the second method, the value of the three raw materials in the first method □ is calculated, and the value of K MSH, that is, the value of calcium aluminate monosal 7 ate hydrate 12) is determined. The mixture of these four components must be set as follows.In other words, if the blast furnace granulated slag or the mixed cement is 601G or more, Calcium silicate is blended in a range below 555 m.

Gypsum and MSH are mixed so that the sum of the amount of MSH converted into dihydrate gypsum plus gypsum (as dihydrate gypsum) is 3091 or less. The conversion of MSH to dihydrate gypsum is as follows.

&7'P, MSHr) Molecular formula 3CaO@AjxOa
``Ca5O<'' ntf12 at 龜H 0.

The relationship between the mixing ratios among the four above is expressed as the total amount of MSH and gypsum as "dihydrate gypsum".

The amount of granulated blast furnace slag or its mixed cement is expressed as "slag-based cement", and the relationship of the mixing ratios among the four above is shown in Figure 1. In other words, Figure 1 shows that MSH and gypsum are considered to be one ``dihydrate gypsum'', and this is combined with granulated blast furnace slag or its mixed cement, which is called ``slag-based cement'', and [)calcium silicate.'' It is a triangular coordinate that shows the relationship between the first and fourth parties based on the relationship between the three parties, and the shaded area in the figure is where the mixing ratio among the four parties should be set. It is hailing the range.

In this invention, the reason why the mixing ratio between the main raw materials is set as described above is as follows. That is, when calcium silicate is blended in an amount exceeding 101, j1! In addition, since calcium silicate is bulky, the specific gravity of the produced inorganic cured product is too small, and the product has insufficient freeze damage resistance. If the amount of calcium silicate is less than 0.5, the effect of accelerating the hardening of the slag will be reduced, and the bulk of the paper product will be low during paper making, resulting in a tendency for excessive sagging.

Next & C, if the blended amount of gypsum or MSf (as dihydrate gypsum) exceeds 30 bags, a large amount of gypsum remains in the system, and the strength upon water absorption immediately decreases.

Water resistance becomes insufficient. In addition, the amount of secondary gypsum is 0.
．． When it is less than 1, it is difficult to see the effect of addition.

Both the first method and the second method use the following raw materials in addition to the one or more raw materials mentioned above. That is, they are reinforcing fibers and other additives added as necessary for manufacturing convenience or to improve the physical properties of the product. As a reinforcing fiber.

Organic or inorganic fibers such as pulp, glass fiber, rock wool, etc. are used, and these should be defibrated before use. This slurry is made into a slurry. Next, this slurry is formed into a desired shape such as a p-plate shape by a paper-making method, cured under heat, and then dried to obtain an uncured product. Excipient method, lI
Fresh conditions and drying conditions are not limited to the neck, but - fresh F14
It is preferable to use a method in which the product is allowed to stand at a temperature of Q to 80°C for 8 hours or more, and then left at room temperature.

-The manufacturing method of the inorganic hardened body according to the present invention-The structure is as shown in Fi's house.-The raw materials for the matrix are granulated blast furnace slag 4 or its vortex, mixed cement, and silicic acid. To prepare calcium dielectric and gypsum by using one or both together with MSH.

During production, the slag hardened quickly (and the obtained inorganic cured product had high strength, small dimensional shrinkage during heat drying, and excellent freeze damage resistance. It is said that the pressability improves.

Product availability has also improved.

Next, examples will be described together with comparative examples.

★An example of the first method will be described together with a comparative example.

All examples use tobermorite as the calcium silicate. This tobermorite was made as follows. Using LCH (incarnate calcium aO) and silicon oxide (Sins) as raw materials, the blending ratio was
/ 5ins = O, -. Then, these were mixed with water and stirred in an autoclave for 21 hours at 80° C. and synthesized from step 1.

The uncured product was produced as follows.

``Original company fees'' in ``1'' as shown in Table 1 below
Water was added and kneaded to make the slurry concentration 8.

In this case, the bulk specific gravity of the inorganic body produced by this formulation is adjusted to around 1.0.

Further, the pulp ti LUKP and the glass fiber were made of alkali-resistant glass. Next, the slurry was made into a paper and pressed to form a shaped body, which was heat cured at 80° C. for 16 hours. After further leaving it in an atmosphere at room temperature for 5 days.

It was dried in an atmosphere at 150° C. for 40 to 50 minutes to obtain a dried inorganic cured plate.

(Margin below) Example 1. Regarding Example 2 and Comparative Example, the following test 1 was conducted during heat curing of the excipients.

The results are shown in Iris 2-.

(Test 1) In this test, the temperature of each excipient was measured as the curing time progressed.

As seen in this WJK, the temperature increase in Examples 1 and 2 was d+ compared to the comparative example. Hydraulic reaction of slag II
Since it is an exothermic reaction, the faster the temperature rise, the faster the hydraulic reaction.

Considering this, it can be seen that the hydraulic reaction of the slag progresses faster in Examples 1 and 2 than in the comparative example. Although omitted in this section, the hydraulic reaction of the slurry proceeded more quickly in other Examples as well as in Examples 1 and 2 compared to the Comparative Examples.

As described above, the following Tests 2 to 4 were conducted on the obtained inorganic cured bodies of all Examples and Comparative Examples.

(Test 2) In this test, the strength t-m was determined for each dry plate when it was dry and when it absorbed water (after being left in water for 24 hours). The size of the drying plate was 5 (m x 12 cm), the span length was 10 cm, and the head speed was 1 m/G. The measurement was performed using an autograph. The results are shown in Table 2.

From Table 2, it can be seen that the Examples have stronger peeling strength when drying and when absorbing water compared to the Comparative Examples.

(IIic test 3) In this test, each sample was left in an atmosphere of 60° C. for 24 hours in drying 41, and the dimensional shrinkage due to drying was measured.

Drying plate size Fi4CmX 16cm T&Dobcon regulator was used. The results are shown in IN3-.

・In this figure, dimensional shrinkage is expressed as dimensional change rate.

The dry layer is abraded at a weight loss rate. The origin was taken after 24 hours. The greater the dimensional shrinkage, the greater the dimensional change rate, and the more the drying progresses, the smaller the weight loss. In other words, the degree of drying can be seen by the weight loss rate. Looking at the same weight reduction rate, all examples (all comparative examples) also have a small dimensional change rate14. Therefore, it can be seen that the dimensional shrinkage due to drying is small.

(Test 4) In this test, Fi and am of each dry plate in the thickness direction were measured. If the swelling ratio is small, it can be said that the material has excellent frost damage resistance. The size of the drying board is r15cm x 12cm! l),
After 40 nits of water-thawing (5°C)-water freezing (-18°C) according to ASTM-B method.

Measurements were made. The results are shown in Summary 3111.

Table 3 From Table 3, it can be seen that all of the examples have a small Jul ratio in the thickness direction, and therefore have excellent frost damage resistance.

As described above, all of the examples of the JII method have faster hydraulic reaction than the comparative examples, and have stronger peeling strength during drying and water absorption, and are superior in one-dimensional stability and frost damage resistance. .

Next, examples of the Iris 20 method will be described together with comparative examples.

Calcium silicate and MSH used in Examples and Comparative Examples
I was surprised as follows. First, calcium silicate is made by kneading the raw materials of the following composition to make a slurry, and then making it into a slurry under a pressure of 10 kg/cm'' gauge pressure in an autotalepe.
Made by stirring for hours. The obtained calcium silicate was in the form of a slurry and was used as it was without drying. 1m-
It was later confirmed that this calcium silicate was dopa-heptalite.

(Blend) Silica ± 57 parts by weight Quicklime 43 parts by weight Water 1600 parts by weight fK and MsB were made into a slurry by kneading the raw materials of the following composition, and reacted in an autoclave at a gauge pressure of 10 and a pressure of □-S for 5 hours. Let me do it.

(Composition) Aluminum hydroxide 28 parts by weight Raw stone R41 parts by weight Dihydrate gypsum 31 parts by weight Water 1000 parts by weight Inorganic hardened body d It was prepared as follows. The raw material composition is as shown in Rattan Table 4. The granulated blast furnace slag has a plain value of 300G, and the pulp is LUKP.

A glass fiber made by Nippon Electric Glass with a cut length of 13 mm was used. Add water to these raw materials and fill
An inorganic cured body was produced in the same manner as the method of Iris.

However, heat curing is at 80℃.

The test was carried out in an atmosphere with a humidity of 9 seconds.

Furthermore, a method was used in which the sample was left at 20° C. in an atmosphere of 95111H for 5 days.

The resulting inorganic cured product was tested for sag strength, zero dimension yield, S, and frost damage resistance thickness *a ratio when dry and water absorbed. Bending strength and freezing damage resistance thickness swelling ratio were measured in the same manner as in Ma I's method, and 1-dimensional shrinkage was measured when the cured product was dried at 60° C. for 24 hours. These results are shown in Table 4 for commuting.

1114 As is clear from the table, all of Example #i had stronger strength during drying and water absorption than Comparative Example.
It has low dimensional shrinkage and excellent frost damage resistance.
・

[Brief explanation of drawings]

Figure 1 shows the triangular seat 11 showing the ratio of raw materials and blending ratio of the JI2 method according to the present invention. Figure 2 shows the relationship between curing time and product temperature in the method of Iris according to this invention. The graphs shown in Figure 3 are the same. Weight loss rate and dimensions of the dried plate in the method of El. Relationship of rate of change 1-
, Arasu Gra-Two de Hi - Patent Applicant Matsushita Electric Works Co., Ltd. Representative Patent Attorney Matsumoto, Takehikokoj 1, Figure 1

Claims (2)

[Claims] (1) Granulated blast furnace slag or its warm cement. A method of obtaining an inorganic hardened material by forming a slurry containing calcium silicate, gypsum and reinforcing fibers and then performing green hardening. The blending ratio among the three parties is 10 parts by weight of calcium silicate or less 1 part of gypsum (
(as dihydrate gypsum) is set so that it is less than 30% by weight, and the remainder is granulated blast furnace slag or its mixed cement.
A method for producing an inorganic cured product characterized by: (2) Granulated blast furnace slag or its mixed cement. Calcium silicate, calcium aluminate mononak
7! -) Shaping a slurry containing hydrate, gypsum and reinforcing fibers, and then curing and curing it] A method for obtaining an inorganic hardened body, which includes granulated blast furnace slag or its warm cement, 〇The blending ratio of calcium aluminate monosulfate hydrate and gypsum is 60-95% by weight for granulated blast furnace slag or its warm cement, 10% by weight for calcium silicate, and 10% by weight for calcium silicate. Convert monosultzate hydrate to dihydrate gypsum and calculate gypsum (as dihydrate gypsum) K
A method for producing an inorganic cured product, characterized in that the total weight of the cured product is set to 30% by weight or less.