TWM660067U - Water-resistant stone - Google Patents

Abstract

The present invention provides a waterproof stone material, which is plate-shaped or column-shaped and comprises a main structure and a plurality of cavities formed therein; the main structure is made of a waterproof material, and the waterproof material comprises a matrix material and modified stone sludge; the modified stone sludge is prepared by the following steps: step (S1): providing stone sludge; step (S2): mixing a modifier, the stone sludge and water, and performing a modification reaction at 50°C to 70°C; the modifier is a cationic surfactant comprising an alkyl group with a carbon number of 10 to 18; the weight ratio of the stone sludge to the modifier is 1000:1 to 1000:50; and step (S3): drying the stone sludge after the modification reaction to obtain the modified stone sludge. The water-resistant stone has better water-resistant properties and compressive strength.

Description

Water-resistant stone

This work is about a type of stone, especially a water-resistant stone.

The stone industry is an important traditional industry closely related to people's livelihood economy and infrastructure. It can be roughly divided into the upstream mining industry, the midstream stone processing industry and the downstream building materials industry, household goods industry and landscape decoration industry. Among them, the stone processing industry refers to the industry that turns natural stone into finished or semi-finished stone through processes such as cutting, carving or grinding. The common types of natural stone include natural raw stones such as granite, marble and serpentine.

Generally speaking, during the cutting and processing of natural stone, a large amount of waste materials such as water-containing stone sludge (also known as stone sludge) and crushed stone scraps (also known as stone scraps) will be generated. Since the processing usually only involves physical processing such as cutting and grinding, the composition of these waste materials is basically the same as that of natural stone. However, since the forms of these waste materials are mostly powder, chips, flakes or blocks, they do not meet the requirements of subsequent applications and cannot be used, resulting in a waste of resources.

In recent years, resource sustainability and resource recycling have become the focus of global attention, and the stone processing industry has also actively sought ways to reuse waste materials to achieve sustainable resource recycling. Therefore, how to give value to stone waste has become an issue worthy of discussion and research, in order to reduce the waste of stone waste and thus comply with the trend of resource sustainability and resource recycling.

In view of the problems existing in the above-mentioned prior art, the purpose of this invention is to provide a water-resistant stone material, the main structure of which uses stone sludge as part of the raw material, so that the stone sludge, which is usually regarded as waste, can obtain the value of recycling; at the same time, the water-resistant stone material of this invention has good water-resistant properties and compressive strength.

To achieve the above-mentioned purpose, the invention provides a water-resistant stone material, which is in the shape of a plate or a column, and comprises a main structure and a plurality of cavities formed in the main structure; the main structure is made of a water-resistant material, and the water-resistant material comprises a base material and a modified stone sludge; wherein the modified stone sludge is prepared by a preparation method comprising the following steps: Step (S1): providing a stone sludge, and the stone sludge comprises granite sludge, marble sludge, serpentine sludge, sludge or a combination thereof; step (S2): mixing a modifier, the stone sludge and water, and performing a modification reaction at 50°C to 70°C; wherein the modifier is a cationic surfactant, and the cationic surfactant contains an alkyl group with a carbon number of 10 to 18; the weight ratio of the stone sludge to the modifier is 1000:1 to 1000:50; and step (S3): drying the stone sludge after the modification reaction to obtain the modified stone sludge.

In some embodiments of the present invention, the thickness of the water-resistant stone can be 1 cm to 500 cm. In other embodiments of the present invention, the shape of the water-resistant stone is a plate, and its thickness can be 1 cm to 30 cm. In other embodiments of the present invention, the shape of the water-resistant stone is a column, and its thickness can be greater than 30 cm and less than or equal to 500 cm.

In some embodiments of the present invention, the waterproof stone is in the shape of a polygonal plate. In other embodiments of the present invention, the waterproof stone is in the shape of a quadrangular plate. In other embodiments of the present invention, the waterproof stone is in the shape of a quadrangular plate, and its length can be 5 cm to 1000 cm, and its width can be 5 cm to 1000 cm.

In some embodiments of the present invention, the water-resistant stone is in the shape of a polygonal column. In other embodiments of the present invention, the water-resistant stone is in the shape of a quadrangular column. In other embodiments of the present invention, the water-resistant stone is in the shape of a quadrangular column, and its length can be 5 cm to 1000 cm, and its width can be 5 cm to 1000 cm.

In some embodiments of the present invention, the water absorption rate of the water-resistant stone after being immersed in water for 24 hours is less than 10%. In other embodiments of the present invention, the water absorption rate of the water-resistant stone after being immersed in water for 24 hours is greater than or equal to 0.5% and less than or equal to 8.5%. In other embodiments of the present invention, the water absorption rate of the water-resistant stone after being immersed in water for 1 hour is greater than or equal to 0.5% and less than or equal to 1.5%. In other embodiments of the present invention, the water absorption rate of the water-resistant stone after being immersed in water for 5 hours is greater than or equal to 2% and less than or equal to 4%. The aforementioned water absorption rate is obtained by immersing about half of the volume of the water-resistant stone in water for testing.

In some embodiments of the present invention, the compressive strength of the water-resistant stone is greater than 185 kilograms per square centimeter (kgf/cm ² ). In other embodiments of the present invention, the compressive strength of the water-resistant stone is greater than or equal to 190kgf/cm ² and less than or equal to 240kgf/cm ² . In other embodiments of the present invention, the compressive strength of the water-resistant stone is greater than or equal to 195kgf/cm ² and less than or equal to 240kgf/cm ² . In other embodiments of the present invention, the compressive strength of the water-resistant stone is greater than or equal to 200kgf/cm ² and less than or equal to 240kgf/cm ² . In some other embodiments of the present invention, the compressive strength of the water-resistant stone is greater than or equal to 220 kgf/cm ² and less than or equal to 240 kgf/cm ² .

According to this invention, the base material can be a general building material, for example, the base material can be cement mortar, but it is not limited thereto. Those with common knowledge in the relevant technical field know that the composition of the cement mortar includes cement, sand and water.

In some embodiments of the present invention, the total weight of the base material is taken as 100 parts by weight, and the amount of the modified stone sludge added can be 1 part by weight to 100 parts by weight. In other embodiments of the present invention, the total weight of the base material is taken as 100 parts by weight, and the amount of the modified stone sludge added can be 1 part by weight to 50 parts by weight. In other embodiments of the present invention, the total weight of the base material is taken as 100 parts by weight, and the amount of the modified stone sludge added can be 1 part by weight to 25 parts by weight. In other embodiments of the present invention, the total weight of the base material is taken as 100 parts by weight, and the amount of the modified stone sludge added can be 1 part by weight to 10 parts by weight.

In some embodiments of the present invention, in the step (S2), the cationic surfactant comprises an amine salt type cationic surfactant, a quaternary ammonium salt type cationic surfactant, or a combination thereof.

In some embodiments of the present invention, in the step (S2), the cationic surfactant comprises an alkyl group with a carbon number of 10 to 15. In other embodiments of the present invention, in the step (S2), the cationic surfactant comprises an alkyl group with a carbon number of 11 to 13.

In some embodiments of the present invention, the amine salt type cationic surfactant is a primary amine salt, and the primary amine salt has the following general formula: R-NH ₃ ⁺ Cl ^- , R is an alkyl group with a carbon number of 10 to 18. In some embodiments of the present invention, R is an alkyl group with a carbon number of 10 to 15; in other embodiments of the present invention, R is an alkyl group with a carbon number of 11 to 13.

In some embodiments of the present invention, in the step (S2), the modification reaction time is 4 hours to 12 hours. In other embodiments of the present invention, in the step (S2), the modification reaction time is 6 hours to 12 hours. In other embodiments of the present invention, in the step (S2), the modification reaction time is 8 hours to 12 hours.

In some embodiments of the present invention, in the step (S1), the stone sludge comprises granite sludge, serpentine sludge or a combination thereof. In some embodiments of the present invention, in the step (S1), the stone sludge comprises granite sludge.

In some embodiments of the present invention, in the step (S2), the weight ratio of the stone sludge to the modifier is 1000:1 to 1000:10. In other embodiments of the present invention, in the step (S2), the weight ratio of the stone sludge to the modifier is 1000:1 to 1000:5.

In some embodiments of the present invention, in the step (S2), the weight ratio of the stone sludge to water may be 1:4 to 1:8. In other embodiments of the present invention, in the step (S2), the weight ratio of the stone sludge to water may be 1:4 to 1:6.

In some embodiments of the present invention, the step (S2) comprises the following steps: step (S2-1): mixing the stone sludge and water to obtain a mixture; and step (S2-2): adding a modifier to the mixture and performing a modification reaction at 50°C to 70°C; wherein the modifier is a cationic surfactant, and the cationic surfactant contains an alkyl group with a carbon number of 10 to 18; the weight ratio of the stone sludge to the modifier is 1000:1 to 1000:50.

According to the invention, the granite mud comprises SiO ₂ , aluminum oxide (Al ₂ O ₃ ), ferric oxide (Fe ₂ O ₃ ), CaO, potassium oxide (K ₂ O), sodium oxide (Na ₂ O), MgO, titanium dioxide (TiO ₂ ), phosphorus pentoxide (P ₂ O ₅ ) and copper oxide (CuO), wherein, based on the total weight of the granite mud, the content of SiO ₂ may be 60 weight percent (wt%) to 70wt%, the content of Al ₂ O ₃ may be 10wt% to 20wt%, the content of Fe ₂ O ₃ may be 1wt% to 10wt%, the content of CaO may be 1wt% to 10wt%, the content of K ₂ The content of O may be 1 wt % to 10 wt %, the content of Na ₂ O may be 1 wt % to 10 wt %, the content of MgO may be 1 wt % to 10 wt %, the content of TiO ₂ may be 0.1 wt % to 1 wt %, the content of P ₂ O ₅ may be 0.1 wt % to 0.5 wt % and the content of CuO may be 0.01 wt % to 0.05 wt %.

According to the present invention, the components of the marble sludge include _SiO2 , _Al2O3 , _{Fe2O3 ,} CaO, _K2O , _Na2O , MgO and _P2O5 , wherein, based on the total weight of the marble sludge _, the content of _SiO2 may be _0.01wt % to _{0.05wt %} , the content of _Al2O3 may be 0.01wt% to 0.05wt%, the content of _Fe2O3 may be 0.01wt% to 0.05wt%, the content of CaO may be 50wt% to 60wt%, the content of _K2O may be 0.005wt% to 0.01wt%, the content of _Na2O may be 0.01wt% to 0.05wt%, the content of MgO may be 1wt% to 10wt% and _the content of _P2O5 may be 0.005wt% to 0.01wt%.

According to the present invention, the components of the serpentine sludge include _SiO2 , _Al2O3 , _Fe2O3 , CaO, _K2O , _Na2O , MgO, _TiO2 and _P2O5 , wherein, based on the _total weight of the marble sludge, the content of _SiO2 may be _1wt % to 10wt _{%, the content of Al2O3 may be 0.1wt% to 1wt%, the content of Fe2O3 may be 1wt} % to 10wt%, the content of _CaO may be 35wt% to 45wt%, the content of _K2O may be 0.1wt% to 0.5wt%, the content of _Na2O may be 0.01wt% to 0.1wt%, the content of MgO may be 10wt% to 15wt%, the content of _TiO2 may be 0.005wt% to 0.01wt% and the content of _P2O3 may be 0.005wt% to 0.01wt% The content of ₅ can be 0.01wt% to 0.05wt%.

In some embodiments of the present invention, in step (S3), the drying step may be drying in an oven at a temperature of 105°C to 115°C for 20 to 24 hours, but is not limited thereto.

In some embodiments of the present invention, in the step (S3), a grinding step and a screening step may be performed after the drying step to obtain the modified stone sludge. The grinding step may be performed by a known grinding method, such as grinding with a grinder or hammering, but is not limited thereto; the screening step may be performed by passing the modified stone sludge after the grinding step through a sieve with an ATSM test screen number of 100 (pore size of about 149 microns to 151 microns) to obtain the modified stone sludge with a pore size of about 151 microns or less.

In this manual, if there is no special indication, the range expressed by "a small number to a large number" means that the range is greater than or equal to the small number and less than or equal to the large number. For example: 50℃ to 70℃ means that the range is "greater than or equal to 50℃ and less than or equal to 70℃".

1: Water-resistant stone

11: Main structure

12: Hollow

A: Local area

S1: Steps

S2: Step

S3: Step

Figure 1A is a schematic diagram of some embodiments of the water-resistant stone of this invention.

FIG. 1B is an enlarged schematic diagram of a local area A of the water-resistant stone shown in FIG. 1A .

Figure 2 is a schematic diagram of the process of preparing the modified stone sludge.

Figure 3 shows the results of the water resistance test of unmodified stone sludge.

Figures 4A to 4C are the results of water resistance tests on modified stone sludge made from different types of stone sludge.

The following is a specific example to illustrate the implementation of this creation. Those who are familiar with this art can easily understand the advantages and effects that can be achieved by this creation through the content of this manual, and make various modifications and changes without violating the spirit of this creation to implement or apply the content of this creation.

Please refer to Figures 1A and 1B, which are used to show and illustrate some embodiments of the present invention. Specifically, as shown in Figure 1A, the shape of the waterproof stone material 1 of the present invention can be a quadrangular plate, and the result of further enlarging and viewing the local area A is shown in Figure 1B, that is, the waterproof stone material 1 includes a main structure 11 and a plurality of cavities 12 formed in the main structure 11; and the main structure 11 is made of a waterproof material, and the waterproof material includes a base material and the aforementioned modified stone sludge.

Please refer to Figure 2, which is a schematic diagram of the preparation process of the modified stone sludge mentioned above, that is, the modified stone sludge used to make the waterproof stone of this invention in the following preparation process is generally prepared according to steps S1 to S3 as shown in Figure 2.

Example 1: Water-resistant stone (granite mud)

First, a proper amount of granite sludge is uniformly mixed with water of about 5 times the weight of the granite sludge to obtain a mixed solution, and then a proper amount of n-dodecylamine hydrochloride (also known as laurylamine hydrochloride, which is an amine salt type cationic surfactant with a chemical formula of CH ₃ (CH ₂ ) ₁₁ NH ₃ ⁺ Cl ^- ) is added to the mixed solution as a modifier and uniformly mixed, and then placed at 50°C for 8 hours for a modification reaction; wherein the weight ratio of the granite sludge to the modifier is 1000:45, and the modifier (solid at room temperature) is preliminarily heated to 80°C in a water-insulated manner to melt it into a liquid state before being added to the mixed solution.

After the modification reaction is completed, the granite sludge that has undergone the modification reaction is taken out and placed in an oven, and dried at a temperature of 110°C for 24 hours for drying, and then the grinding step and the screening step are continued to obtain the modified granite sludge. The grinding step is performed by hammering. The screening step is performed by using a screen with ATSM test screen number 100 (screen hole is about 149 microns).

Next, 200 grams of cement, 600 grams of sand and 126 grams of water are uniformly mixed to obtain a cement mortar as a base material, and then 40 grams of the modified granite mud mentioned above are added thereto to obtain a waterproof material. Then, the waterproof material is filled into a mold with a length of 16 cm, a width of 16 cm and a height of 4 cm, and then left to solidify and form, thereby obtaining the waterproof stone of Example 1. The waterproof stone of Example 1 is in the shape of a square plate (16 cm in length, 16 cm in width and 4 cm in height), and has a main structure and a plurality of cavities formed in the main structure, and the main structure is made by solidifying the waterproof material.

Example 2: Water-resistant stone (marble sludge)

The preparation process of the water-resistant stone of Example 2 is similar to that of Example 1, and the main difference is that Example 2 uses marble sludge, and the modification reaction is carried out under the condition that the weight ratio of the marble sludge to the modifier is 1000:2. Except for the above differences from Example 1, the rest is the same process as Example 1 to obtain the water-resistant stone of Example 2.

Example 3: Water-resistant stone (serpentine silt)

The preparation process of the water-resistant stone of Example 3 is similar to that of Example 1, and the main difference is that Example 3 uses serpentine silt, and the modification reaction is carried out under the condition that the weight ratio of the serpentine silt to the modifier is 1000:7. Except for the above differences from Example 1, the rest is in accordance with the same process as Example 1 to obtain the water-resistant stone of Example 3.

Comparison Example 1: Cement Mortar Stone

200 grams of cement, 600 grams of sand and 126 grams of water are uniformly mixed to obtain a cement mortar. Then the cement mortar is filled into a mold with a length of 16 cm, a width of 16 cm and a height of 4 cm, and then left to solidify and form, thereby obtaining the cement mortar stone of Comparative Example 1. The cement mortar stone of Comparative Example 1 is in the shape of a square plate (length of 16 cm, width of 16 cm and height of 4 cm), and it has a main structure and a plurality of cavities formed in the main structure, and the main structure is made by solidifying the cement mortar.

Test Example 1: Water resistance test

Test Example 1 uses the modified granite sludge in the preparation process of Example 1, the modified marble sludge in the preparation process of Example 2, the modified serpentine sludge in the preparation process of Example 3, and the unmodified marble sludge as test samples for testing. Specifically, different test samples of approximately equal weight are placed in different containers, and then a few drops of water are dropped on the surface of the test samples with a dropper, and the changes of the water drops are observed after standing for a period of time. The results of Examples 1 to 3 and the unmodified marble sludge are shown in Figures 4A to 4C and Figure 3, respectively.

Please refer to Figure 3 first. The position where the water drop was originally dripped on the surface of the unmodified marble sludge (as indicated by the arrow in the figure) has no water drop, which means that the water drop has penetrated into it, showing that the unmodified marble sludge is not water-resistant. Looking at Figures 4A to 4C again, water droplets can be observed on the surface of the test samples of Examples 1 to 3 (as indicated by the arrow in the figure), which means that the water droplets are blocked on the surface and cannot penetrate into it, showing that the modified granite sludge in the preparation process of Example 1, the modified marble sludge in the preparation process of Example 2, and the modified serpentine sludge in the preparation process of Example 3 are indeed water-resistant.

Test Example 2: Water absorption test

Test Example 2 uses the water-resistant stones of Examples 1 to 3 and the cement mortar stone of Comparative Example 1 for testing. Specifically, the weight of the water-resistant stones of Examples 1 to 3 and the cement mortar stone of Comparative Example 1 was first measured, and then according to the content of CNS 3763, a standard method for cement waterproofing agents, about half of the volume of the water-resistant stones of Examples 1 to 3 and the cement mortar stone of Comparative Example 1 was immersed in water under the condition of controlling the environmental conditions to be 23±2°C and the relative humidity to be greater than 95%, and each group was taken out and weighed after being immersed for 1 hour, 5 hours and 24 hours, respectively, so that the water absorption of different groups after being immersed in water for different times can be obtained, and the water absorption rate of different groups at different times of immersion in water can be calculated, and the results are listed in Table 1 below. The water absorption is obtained by the following formula: the total weight of the sample taken out after soaking in water for different time periods - the total weight of the sample before the test; and the water absorption rate is obtained by the following formula: (the water absorption measured after soaking in water for different time periods / the total weight of the sample before the test) × 100%.

From the results in Table 1 above, it can be seen that the weight (i.e., dry weight) of the water-resistant stones of Examples 1 to 3 and the cement mortar stone of Comparative Example 1 before the test is roughly the same. However, after each group was immersed in water for 1 hour, the water absorption of the cement mortar stone of Comparative Example 1 was as high as 40.8 grams, and its water absorption rate was 8.34%. In comparison, the water absorption of Examples 1 to 3 was only 4.6 grams, 5.7 grams, and 4.4 grams, respectively, and the water absorption rates were only 0.91%, 1.16%, and 0.90%, respectively. It can be seen that when immersed in water for a short time (e.g. 1 hour), the water absorption or water absorption rate of the water-resistant stone materials of Examples 1 to 3 are much lower than the water absorption and water absorption rate of the cement mortar stone materials of Comparative Example 1. It is obvious that the water-resistant stones of Examples 1 to 3 do show excellent water-resistant properties in a short time.

Looking at the results after immersion in water for 5 hours and 24 hours, even though the water absorption and water absorption rate will gradually increase with the increase of immersion time in water, compared with the result of comparative example 1, Examples 1 to 3 still have lower water absorption and water absorption rate. Among them, the water-resistant stone of Example 3 still has excellent results of only 30.7 grams and 6.1% respectively even after immersion in water for 24 hours. It can be seen that even when immersed in water for a long time (such as 5 hours and 24 hours), the water absorption or water absorption rate of the water-resistant stone of Examples 1 to 3 is still lower than that of the cement mortar stone of Comparative Example 1, indicating that the water-resistant stone of Examples 1 to 3 can also show good water-resistant properties for a long time.

From this, we can see that compared to simple cement mortar stone, the waterproof stone of this creation does have good waterproof properties.

Test Example 3: Compressive Strength Test

Test Example 3 is a test sample prepared in accordance with the process of Examples 1 to 3 and Comparative Example 1. The main difference is that when preparing the test samples of Examples 1 to 3, after the waterproof material is filled into the mold, a 28-day static curing step is performed, and then the test samples of Examples 1 to 3 are obtained; and when preparing the test sample of Comparative Example 1, after the cement mortar is filled into the mold, a 28-day static curing step is also performed, and then the test sample of Comparative Example 1 is obtained. Specifically, the test samples of Examples 1 to 3 and Comparative Example 1 were placed on a compression tester (manufacturer: HCH Enterprise Co., Ltd. (HCH), model: HCH-239-20T), and the compressive strength of each group was measured according to CNS 1010-hydraulic cement slow material compressive strength test method. The results are listed in Table 2 below.

From the results in Table 2 above, it can be seen that the compressive strength of Comparative Example 1 is only 183.1kgf/cm ² , while the compressive strengths of Examples 1 to 3 are 230.7kgf/cm ² , 195.5kgf/cm ² and 219.6kgf/cm ² , respectively. It is obvious that Examples 1 to 3 all have significantly higher compressive strengths than Comparative Example 1, and Example 1 has the highest compressive strength of 230.7kgf/cm ² .

From this, we can see that compared to simple cement mortar stone, the waterproof stone of this creation does have better compressive strength.

In summary, the main structure of the water-resistant stone of this creation is made of stone sludge as part of the raw material, so that the stone sludge, which is usually regarded as waste, can obtain the value of recycling; at the same time, the water-resistant stone of this creation has good water-resistant properties and compressive strength.

1: Water-resistant stone

A: Local area

Claims (10)

A water-resistant stone material, which is in the shape of a plate or a column, and comprises a main structure and a plurality of cavities formed in the main structure; the main structure is made of a water-resistant material, and the water-resistant material comprises a base material and a modified stone sludge; Wherein, the modified stone sludge is prepared by a preparation method comprising the following steps: Step (S1): providing a stone sludge, the stone sludge comprising granite sludge, marble sludge, serpentine sludge or a combination thereof; Step (S2): Mix a modifier, the stone sludge and water, and perform a modification reaction at 50°C to 70°C; wherein the modifier is a cationic surfactant, and the cationic surfactant contains an alkyl group with a carbon number of 10 to 18; the weight ratio of the stone sludge to the modifier is 1000:1 to 1000:50; and Step (S3): Dry the stone sludge after the modification reaction to obtain the modified stone sludge. The water-resistant stone as described in claim 1, wherein the thickness of the water-resistant stone is 1 cm to 500 cm. The water-resistant stone as described in claim 1, wherein the water-resistant stone is in the shape of a polygonal column. The water-resistant stone as described in claim 3, wherein the water-resistant stone is in the shape of a quadrangular column. The water-resistant stone as described in claim 4, wherein the length of the water-resistant stone is 5 cm to 1000 cm. The water-resistant stone as described in claim 4, wherein the width of the water-resistant stone is 5 cm to 1000 cm. The water-resistant stone as described in claim 1, wherein the water-resistant stone is in the shape of a polygonal plate. The water-resistant stone as described in claim 7, wherein the water-resistant stone is in the shape of a square plate. The water-resistant stone as described in claim 8, wherein the length of the water-resistant stone is 5 cm to 1000 cm. The water-resistant stone as described in claim 8, wherein the width of the water-resistant stone is 5 cm to 1000 cm.