TWM666451U - Pozzolanic product - Google Patents

Abstract

The present application provides a pozzolanic product, which includes: a body having a predetermined shape; and a plurality of porous structures, evenly disposed inside the body and having a pozzolanic material encapsulated therein. Wherein, the pozzolanic material is prepared by the following steps: collecting waste glass; crushing the waste glass into waste glass particles with a predetermined size; and grinding the waste glass particles to obtain finely ground glass powder with a predetermined particle size and a predetermined particle size distribution as the pozzolanic material.

Description

Products

The present application relates to a glass product, in particular to a glass product made from waste glass that has been activated.

Taiwan's buildings mainly use reinforced concrete building materials. These materials are energy-intensive and have high carbon emissions. Concrete is the most used, consuming more than 10 million tons of cement each year, and the production of one ton of cement clinker will generate about 0.9 to 1.0 tons of carbon dioxide emissions. Therefore, in order to reduce carbon emissions and achieve the Net Zero goal, it is necessary to consider reducing the use of concrete or improving the amount of cement in the concrete formula. However, how to effectively reduce the amount of cement while maintaining safety, workability and durability is an important issue in the current construction industry. In the existing technology, it has been found that Pozzolanic material can be used to replace part of the cement clinker to achieve the purpose of reducing the amount of cement in concrete.

"Pozzolanic material" refers to a substance that has only a little or no cementitious property, but can react with calcium hydroxide (Ca(OH) ₂ ) in cement hydration products to form a product with cementitious properties under sufficient humidity. This reaction is called the "Pozzolanic reaction", which is also known as the "secondary hydration cementation reaction".

Common ash materials include coal fly ash and silica ash, which have very different chemical compositions and physical properties. Fly ash from coal-fired power plants mainly consists of silicon dioxide (SiO ₂ ) and aluminum oxide (Al ₂ O ₃ ). Silica ash, also known as fine silicon dioxide, is a byproduct of the iron-silicon alloy smelting process. Its main component is amorphous silicon dioxide. Among them, silica ash has a higher ash activity index, while coal fly ash has a relatively low ash activity.

In recent years, glass is not biodegradable and cannot be decomposed by landfill or composting. In addition, it is non-flammable, so recycling its resources is currently the best treatment method. Since the main component of waste glass on the market is amorphous silicon dioxide, it can react with cement when added to cement, and it has begun to be adopted by the construction industry. Waste glass mainly comes from glass containers, flat glass, and TFT-LCD liquid crystal substrate glass. In addition, with the increase in demand for solar photovoltaics, the amount of waste glass processed by solar photovoltaic panels will also increase accordingly in the future.

At present, waste glass can be used as engineering aggregate after screening, crushing, and impurity removal, and is mostly used in recycled products such as asphalt paving, bricks, and cement products. However, most of these applications are downgraded use of material recycling, and fail to fully utilize the high silicon and high glass content of waste glass. Previous related technologies such as patents CN103553491A and CN103172323A only disclose the preparation method of waste glass for concrete, but do not explore the activity of waste glass. In addition, although patents TWI761284 and TWI796036 propose to react and activate glass powder with an alkali initiator to form a new type of cement-free inorganic binder or inorganic solidifier, the use of an alkali initiator will increase production costs, and its commercial application has yet to be verified, and market acceptance is relatively low.

Therefore, in order to solve the problems of insufficient activity of waste glass, low recycling rate and insufficient concrete performance when waste glass is used as a concrete material to make products in the existing technology, it is urgent to develop a method to improve the bonding activity of waste glass to increase its recycling rate and create high added value, which is an important goal of current technological development.

Based on the above reasons, the present application provides a glass product, which includes: a body having a predetermined shape; and a plurality of pore structures, which are evenly arranged inside the body and have glass material coated therein. The glass material is prepared by the following method: collecting waste glass; crushing the waste glass into waste glass particles of a predetermined size; and grinding the waste glass particles to obtain finely ground glass powder with a predetermined particle size and a predetermined particle size distribution, so as to serve as the glass material.

Preferably, the predetermined shape of the body may include circular, square, conical, arched, spherical, cylindrical or any shape designed according to requirements.

Preferably, the molded product can be a building, a decoration, a container or a mold.

Preferably, the cement product may further include cement.

Preferably, the concrete product may further include concrete or cement mortar.

Preferably, the predetermined size of the waste glass particles may be less than about 10 mm.

Preferably, the predetermined particle size of the finely ground glass powder may be less than about 45 μm.

Preferably, the predetermined particle size distribution of the finely ground glass powder may be such that the residue is less than about 5%.

Preferably, the finely ground glass powder is further treated with a chemical additive.

Preferably, the chemical auxiliary agent may include diethylene glycol, triethanolamine, triisopropanolamine or any combination thereof.

Preferably, the finely ground glass powder may have a predetermined specific surface area, preferably about 2500 cm ² /g to about 8000 cm ² /g.

Preferably, the waste glass may come from glass containers, flat glass, solar photovoltaic panel glass, TFT-LCD liquid crystal substrate glass or any combination thereof.

Preferably, the method further comprises screening the waste glass according to the type and/or color before the crushing step and/or before the grinding step.

In another aspect of the present application, a blast furnace material prepared by the above method is provided. Preferably, the blast furnace material further comprises coal fly ash, silica ash or a combination thereof.

In order to achieve the above-mentioned purpose, the present application adopts the following technical solution: waste glass is crushed, ground and activated to form a highly active cementitious material, thereby increasing its addition ratio in cement concrete and improving the fresh mix performance and hardening performance of concrete to prepare cementitious products.

Definition

The term "cement" used in this article refers to a building material, which is a hydraulic cement obtained by grinding clinker with hydraulic crystalline calcium silicate as the main component. When cement is mixed with water, a hydration reaction occurs to produce calcium silicate hydrate (C-S-H) and calcium hydroxide (Ca(OH)₂).

The term "hydration reaction" in this article refers to the chemical reaction between the components of cement such as tricalcium silicate (C₃S) and dicalcium silicate (C₂S) and water when cement is mixed with water to form hydration products such as calcium silicate hydrate (C-S-H) and calcium hydroxide (Ca(OH)₂). Calcium silicate hydrate (C-S-H) gradually forms and forms a strong structure, giving concrete good mechanical properties and durability.

The term "Bozulan reaction" herein refers to a chemical reaction occurring in cement-based materials, involving the reaction between Bozulan materials (such as coal fly ash, silica ash, or ground glass powder in this article) and calcium hydroxide (Ca(OH)₂) generated by cement hydration. Specifically, amorphous silica (SiO₂) in Bozulan materials reacts with Ca(OH)₂ in the presence of water to generate additional calcium silicate hydrate (C-S-H), which can fill the microscopic channels of cement paste, refine the pores, and improve water tightness, thereby improving the compressive strength, density and durability of concrete, cement mortar or cement products, and improving their later strength.

The term "grinding and grading system" in this article refers to the process of feeding raw materials (such as waste glass particles) into a grinding mill for grinding. The grinding mill can be a ball mill, vertical roller mill, ring roller mill or Raymond mill. The process can choose continuous feeding and discharging, or a certain weight of raw materials can be fed in at one time for grinding. After grinding, the material will enter the micro powder classifier for particle size control. The material with finer particle size will be output as the final product, while the material with coarser particle size will return to the grinding mill for re-grinding until the required particle size is achieved.

The term "waste glass particles" herein refers to waste glass having a predetermined size obtained by only undergoing the crushing process of this application but without being ground by a grinding and grading system (hereinafter referred to as "physical activation") and treated with chemical agents (hereinafter referred to as "chemical activation").

The term "finely ground glass powder" herein refers to the waste glass particles having a predetermined particle size and a predetermined particle size distribution prepared after the waste glass particles are further subjected to the physical activation and/or chemical activation steps of the present application.

The term "activity index" in this article refers to the ability of the aforementioned finely ground glass powder to undergo secondary reaction with calcium hydroxide (Ca(OH)₂) produced after cement hydration when used as a grouting material. The activity index is an indicator for evaluating the activity of grouting materials. It represents the ratio of the compressive strength of the grouting material mixed with cement mortar (test group) to the pure cement mortar (control group) at a certain mixing ratio (usually 20% of the weight of cement replaced by the grouting material). The higher the value, the greater the contribution of the grouting material to improving the compressive strength of the mixture. This test method is based on the relevant provisions of CNS 10896 "Method for sampling and testing of fly ash or natural pozzolans for use as a mineral admixture in portland-cement concrete".

The term "screening residue" herein refers to the ratio of the finely ground glass powder remaining on the screen after the finely ground glass powder is screened through a screen with a predetermined aperture to the total finely ground glass powder before screening.

The term "about" herein modifies a term or value so that it is not an absolute value, but cannot be found in the prior art. In some embodiments, "about" covers values within 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% (including such values) of the measured value or any intermediate range (e.g., ±2% to 6%). This includes at least the degree of expected experimental error, technical error, and instrumental error of the method, analysis or measurement value.

Embodiment

See FIG. 1, which is a flow chart of a method for preparing a glass material according to an embodiment of the present application. The preparation method includes step S11: collecting waste glass; step S12: crushing the waste glass into waste glass particles of a predetermined size, the predetermined size is preferably less than about 10 mm, more preferably less than about 8 mm, and even more preferably less than about 5 mm; step S13: grinding (physical activation) the waste glass particles by a grinding and grading system to obtain finely ground glass powder with a predetermined particle size and a predetermined particle size distribution; the predetermined particle size must be less than about 75 μm, preferably less than about 45 μm, more preferably less than about 35 μm, and even more preferably less than about 25 μm. The predetermined particle size distribution is preferably less than about 5%, more preferably less than about 3%, and even more preferably less than about 1%, so as to be used as a raw material; (if necessary) step S14: further chemically activating the finely ground glass powder using a chemical additive.

In one embodiment, before the crushing step and/or the grinding step, the waste glass is further screened according to the type and/or color, for example, into colorless transparent glass and colored glass. The screening method may include but is not limited to magnetic separation, air separation or screening.

In one embodiment, the chemical activation method uses one or any combination of chemical aids such as diethylene glycol, triethanolamine, triisopropanolamine as a surface modifier to improve the charge dispersion on the surface of waste glass particles, thereby enhancing the hydration reaction. The addition ratio can be appropriately adjusted as needed (for example, 0.035% of the weight of finely ground glass powder).

In one embodiment, the finely ground glass powder prepared by the method of the present application has a predetermined specific surface area, preferably about 2500 cm ² /g to about 8000 cm ² /g, more preferably about 3000 cm ² /g to about 6000 cm ² /g.

In one embodiment, the waste glass used may come from glass containers, flat glass, solar photovoltaic panel glass, glass electronic screens, etc. According to the main components, it may be sodium calcium glass, borosilicate glass, or quartz glass, etc.; according to the type of glass, it may be ordinary glass or reinforced glass, etc.

In one embodiment, the quartz crystal material prepared by the method of FIG. 1 may include not only finely ground glass powder but also common coal fly ash, silica ash, etc.

Refer to Figures 2 and 3, which are schematic diagrams of a Buzulan product according to one embodiment of the present application. As shown in the figure, the Buzulan product 2 includes a main body 21 with a predetermined shape and a plurality of porous structures 23 uniformly arranged inside the main body 21 and having a finely ground glass powder 22 as the Buzulan material of the present application coated therein. The main body 21 can be designed into any shape according to the needs of the user or the builder, such as a two-dimensional or three-dimensional circular, square, conical, arched, spherical, cylindrical or irregular shape. In one embodiment, the Buzulan product 2 can further include a cementitious material such as cement. In one embodiment, the Buzulan product 2 can further be concrete or cement mortar. The Buzulan product 2 can be, for example, a building, a decoration, a container or a mold.

Examples

Materials and methods

The sources of waste glass may include container glass, flat glass, solar photovoltaic panels and/or TFT-LCD liquid crystal substrate glass. Container glass and flat glass may come from waste glass generated by glass recycling and processing institutions, while solar photovoltaic panel glass may come from waste solar photovoltaic panel processing institutions, or from waste electronic components, scraps and defective products in the solar photovoltaic panel manufacturing process; TFT-LCD liquid crystal substrate glass comes from waste glass substrates used in the TFT-LCD manufacturing process.

The collected waste glass is sorted by type and/or color, crushed, and processed to obtain high-purity waste glass particles; then the waste glass particles are physically activated into finely ground glass powder through a grinding and grading system, and chemical activation methods are used as needed to increase the specific surface area (fineness) of the waste glass particles, thereby forming a highly active working material.

Scrap glass grindability test

Waste glass of the same source and quality was uniformly crushed to less than 5 mm by a crusher, and then the waste glass particles were put into a ball mill for grinding. After setting different grinding times (20 minutes, 40 minutes, 60 minutes, and 80 minutes), the sieve residue of the finely ground glass powder that did not pass through the 45 µm sieve (hereinafter referred to as "45 µm sieve residue") was measured. The smaller the value, the more uniform the particle size distribution of the finely ground glass powder, and the 45 µm sieve residue reaching less than about 5% is the expected value (detailed example A). The results of different grinding times on the 45 µm sieve residue are shown in Table 1.

Table 1 Finely ground glass powder Grinding time 20 minutes 40 minutes 60 minutes 80 minutes 45 µm Screening 38% 9.9% 5.1% 2.8%

Since the Mohs hardness of glass is 6, which is only slightly lower than quartz (hardness 7) and higher than limestone (hardness 3), waste glass is a material that is difficult to grind. From the test results of waste glass grindability in Table 1, it can be seen that physical activation methods are needed to improve the grinding fineness and particle size distribution of waste glass particles in order to obtain the desired finely ground glass powder.

Activity index of finely ground glass powder used in cement

Example A

The same source and same quality of finely ground glass powder, according to the CNS 10896 test method (as a cementing material and replacing 20% of the weight of cement), the results of the 45 µm sieve residue test on the activity index at different grinding times are shown in Table 2, showing that the activity index increases as the 45 µm sieve residue decreases. When the grinding time is 60 minutes, the 45 µm sieve residue of the finely ground glass powder is the expected 5.1%, at which time the 28-day activity index can reach about 85% of the control group, which has a good cementing reaction, as shown in test group C. If the grinding time is extended to 80 minutes, the 45 µm sieve residue of the finely ground glass powder is only 2.8%, at which time it has the best activity index display, as shown in test group D. Therefore, after physical activation of waste glass, the particle size distribution of the finely ground glass powder will be a key factor affecting the activity index. Considering that the activity index of the test group has reached more than 85% of the control group, the 45 µm screen residue of the finely ground glass powder should be less than about 5% as the expected value.

Table 2 No. Finely ground glass powder (45 µm sieve residue) Activity index (kgf/cm ² ) Fluidity value (%) 7 days 14 days 28 days Control group (pure cement mortar) - 340 (100%) 379 (100%) 431 (100%) 105.5 Test Group A (grinding for 20 minutes) 38 % 252 (74%) 283 (75%) 316 (73%) 120 Test Group B (grinding for 40 minutes) 9.9% 246 (72%) 269 (71%) 323 (75%) 115.5 Test Group C (grinding for 60 minutes) 5.1% 240 (71%) 304 (80%) 367 (85%) 115 Test Group D (grinding for 80 minutes) 2.8% 289 (85%) 342 (90%) 404 (94%) 117

Example B

The activity index test results of fine-ground glass powder with the same source, quality and grinding time under different chemical activation methods according to the CNS 10896 test method are shown in Table 3, which shows that the use of different types of chemical additives will affect the activity index and 45 µm sieve residue of fine-ground glass powder. Among them, test groups E to G (using a combination of chemical additives, whose main components are (a) diethylene glycol, (b) triethanolamine and (c) triisopropanolamine) can effectively improve the grinding efficiency of waste glass (i.e., the 45 µm sieve residue is reduced) and further improve the activity index of fine-ground glass powder as a raw material. In contrast, the control groups H and I (using a combination of chemical additives, whose main components are (d) isopropyl alcohol: ethylene glycol = 1:1 and (e) sodium acrylate: sodium sulfate: sodium silicate = 17:2:1) have little effect on the grinding efficiency of waste glass, resulting in the activity index of test groups H and I being similar to or even lower than that of test group D without adding chemical additives. The results show that the appropriate selection of chemical additives (such as combinations (a), (b), and (c)) can effectively improve the grinding efficiency of waste glass and increase its activity index as a waste glass material.

Table 3 No. Finely ground glass powder (45 µm sieve residue) Activity index (kgf/cm ² ) Fluidity value (%) 7 days 14 days 28 days Control group (pure cement mortar) - 340 (100%) 379 (100%) 431 (100%) 105.5 Test Group D (grinding only (80 min)) 2.8% 289 (85%) 342 (90%) 404 (94%) 117 Test Group E (Grinding + Chemical Additive Combination a) 0.8% 279 (82%) 350 (92%) 410 (95%) 113 Test Group F (Grinding + Chemical Additive Combination b) 0.6% 305 (90%) 350 (92%) 418 (97%) 118 Test Group G (Grinding + Chemical Additive Combination C) 0.9% 298 (88%) 348 (92%) 426 (99%) 118 Control group H (grinding + chemical additive combination d) 1.6% 279 (82%) 322 (85%) 384 (89%) 121 Control group I (grinding + chemical additive combination e) 2.7% 264 (78%) 297 (78%) 375 (87%) 119

Example C

The test results of finely ground glass powder and activity index of different waste glass types with the same mass, same grinding time and same chemical activation method according to the CNS 10896 test method are shown in Table 4. The 45 µm sieve residue of finely ground glass powder produced from four waste glass sources is less than 5%, its specific surface area is 3300~5790 ^cm2 /g, and its activity index (28 days) is 95~105%, indicating that after the physical activation and chemical activation treatment of this application, finely ground glass powder of different waste glass types can be used as highly reactive raw materials and can be effectively used in cement products or cement concrete.

Table 4 Test No. Finely ground glass powder (45 µm sieve residue) Specific surface area (cm ² /g) Activity index (kgf/cm ² ) Fluidity value (%) 7 days 14 days 28 days Control group (pure cement mortar) - - 340 (100%) 379 (100%) 431 (100%) 105.5 Test Group J (Container Glass) 0.8% 3,780 301 (89%) 349 (92%) 425 (99%) 117 Test Group K (Flat Glass) 0.5% 4,210 305 (90%) 356 (94%) 435 (101%) 115 Test Group L (Solar Photovoltaic Panel Glass) 1.7% 3,300 289 (85%) 342 (90%) 410 (95%) 113 Test Group M (TFT-LCD Liquid Crystal Substrate Glass) 0.2% 5,790 328 (96%) 392 (103%) 452 (105%) 115

Activity index of finely ground glass powder used in concrete

In this experiment, the solar photovoltaic panel glass was ground and graded by physical activation and chemical activation methods to generate finely ground glass powder with a screen residue (45 µm) of less than 5%, which replaced 15% of the cement weight. Compared with container glass and flat glass, since solar photovoltaic panel glass is a type of reinforced glass, the finely ground glass powder produced by using solar photovoltaic panel glass has a wider particle size distribution and a slightly lower specific surface area under the same physical activation and chemical activation methods, but its 45 µm screen residue can still be controlled within 5%.

The results of the strength test of Portland limestone cement (IL) concrete using finely ground glass powder of the same mass, same grinding time and same chemical activation method are shown in Figure 4. The test results show that the concrete produced using finely ground glass powder as a concrete material can reach an activity index of about 94% of the control group (concrete using pure cement mortar) at 28 days. This shows that the finely ground glass powder treated by physical activation and chemical activation in this application has a strength close to that of traditional cement in IL concrete and can partially replace cement. It is a low-carbon, highly reactive concrete material that can be effectively used in cement products or cement concrete.

Conclusion

Observation of the finely ground glass powder produced by waste glass in this application shows that waste glass can effectively improve its activity index after appropriate physical activation and/or chemical activation treatment. When applied to cement and concrete, it can reach an activity index of more than 85% in 7 days and more than 95% in 28 days compared to traditional cement. It can be seen that the particle size and particle size distribution of finely ground glass powder is one of the main factors affecting the activity index.

According to the experimental results of the above examples of this application, at least the following advantages can be proved: 1. This application can effectively solve the problem that the adhesive activity of waste glass as a grouting material is insufficient, resulting in insufficient concrete performance. 2. This application uses activated finely ground glass powder as a grouting material, which can not only improve the recycling rate of waste glass, but also add the finely ground glass powder to concrete to replace part of the cement to reduce the amount of cement added. 3. The finely ground glass powder of this application is waste glass with a predetermined particle size and a predetermined particle size distribution, which can react well with cement clinker to effectively improve the working performance of concrete, thereby creating high added value.

Many features and advantages of the present application are obvious from the specification, and therefore, the attached patent scope is intended to cover all features and advantages that fall within the true spirit and scope of the present application. In addition, since a person with ordinary knowledge in the field will easily associate with various modifications and changes, the present application is not limited to the explicit process, structure and operation shown and described, and all suitable modifications and equivalents fall within the scope of the present application.

In addition, those with ordinary knowledge in the art will appreciate that the concept of the present application can be easily used as the basis for other methods, structures and systems to achieve the multiple purposes of the present application. Therefore, the scope of the attached patent application should not be considered to be limited by the description in the specification.

S11~S14: Step 2: Making the product 21: Body 22: Finely ground glass powder 23: Porous structure

FIG. 1 is a flow chart of a method for preparing a quartz crystal material according to an embodiment of the present application.

FIG. 2 is a schematic diagram of a product according to an embodiment of the present application.

FIG3 is a schematic cross-sectional view of the product of FIG2 according to an embodiment of the present application.

FIG. 4 is a result of an activity test of finely ground glass powder applied to Portland limestone cement (IL) cement concrete according to an embodiment of the present application.

2: Products made by Buzuolan

21: Body

22: Finely grind waste glass powder

23: Porous structure

Claims (15)

A glass product, comprising: a body having a predetermined shape; and a plurality of pore structures, which are uniformly arranged inside the body and have glass material coated therein, wherein the glass material is prepared by the following method: collecting waste glass; crushing the waste glass into waste glass particles of a predetermined size; and grinding the waste glass particles to obtain finely ground glass powder of a predetermined particle size and a predetermined particle size distribution, to serve as the glass material. As in claim 1, the predetermined shape comprises a circle, a square, a cone, an arch, a sphere, a column or any shape designed according to requirements. For example, the manufactured product as claimed in claim 2 includes a building, a decoration, a container or a mold. The product as claimed in claim 1 further comprises cement. The product as claimed in claim 1 further comprises concrete or cement mortar. The article of manufacture of claim 1, wherein the predetermined size of the waste glass particles is less than about 10 mm. The article of manufacture of claim 1, wherein the predetermined particle size of the finely ground glass powder is less than about 45 µm. The product of claim 1, wherein the predetermined particle size distribution of the finely ground glass powder is a screen residue of less than about 5%. The product as claimed in claim 1, wherein the finely ground glass powder is further treated with a chemical additive. The product of claim 9, wherein the chemical auxiliary agent comprises diethylene glycol, triethanolamine, triisopropanolamine or any combination thereof. The product as claimed in claim 1, wherein the finely ground glass powder has a predetermined specific surface area. The article of claim 11, wherein the predetermined specific surface area is about 2500 cm ² /g to about 8000 cm ² /g. The product as claimed in claim 1, wherein the waste glass comes from glass containers, flat glass, solar photovoltaic panel glass, TFT-LCD liquid crystal substrate glass or any combination thereof. A product as claimed in claim 1, wherein the method further comprises screening the waste glass according to the type and/or color before the crushing step and/or before the grinding step. The quartz product of claim 1, wherein the quartz material further comprises coal fly ash, silica ash or a combination thereof.