TW202007672A - Manufacturing method of steel slag cementitious material - Google Patents

Abstract

The present invention relates to a manufacturing method of a steel slag cementitious material. It comprises the steps of (a) prepating oxidizing slag powder or reductive slag powder; and (b) mixing 0-70 wt% of the oxidizing slag powder or the reductive slag powder with the remaining weight percent of a cement clinker or/and power plant fly ash to obtain the steel slag cementitious material. Accordingly, the present invention achieves low cost and resource recycling by utilizing industrial waste to produce the steel slag cementitious material which meets the requirements of cement setting time, compressive strength and dry shrinkage rate.

Description

Method for manufacturing steel ballast cement

The invention relates to a method for manufacturing steel ballast cement, in particular to a method for manufacturing steel ballast cement by using oxidized ballast powder, reduced ballast powder and power plant fly ash in industrial waste, which can be used under normal temperature environment It is obtained by mixing dry, without high-temperature firing, without adding water during the mixing process, and can meet the requirements of cement setting time, compressive strength and dry shrinkage.

According to the vigorous development of my country's iron and steel industry, product grades have gradually increased, and production has also increased year by year. However, a large amount of by-product slag is also produced in the steelmaking process. Early slag was regarded as worthless waste, but based on the rapid expansion of the quantity, it is currently a research key project in various steel-producing countries in the world. The annual output of domestic electric arc furnace steel-making slag can reach 1 million tons, and most of them are currently used as filling materials and road base laying materials, and the economic value is not high. Since this steel-making residue is similar to cement and water-quenched furnace powder, it is used as a raw material for steel slag cement, construction and decoration in major steel-making countries such as Japan and the mainland. In addition to increasing its use value, its purpose is also hoped to be resolved Increasing waste disposal issues.

For example, Chinese Patent Publication No. CN102503204A discloses “a road material made of steel slag”, which mainly contains fine steel slag, slag powder and stone material or solid steel slag as steel-making solid waste steel slag, which is characterized in that steel slag is generated when it meets water The characteristics of calcium hydroxide stimulate the granulated blast furnace slag powder to produce a gelation effect, and the mixture is cemented and solidified. The slag powder mixed with fine steel slag is used as a stabilizer, and the fine steel slag can also be used as fine aggregate to improve the durability of the road base and Compression resistance, which can achieve the use of iron and steel associated resources to replace the existing technology using lime and cement as the road base material; however, the above materials need to add water and add steelmaking waste fine steel slag, slag powder, and then add stone or crude steel The slag can be mixed uniformly in a certain proportion to obtain a mixed material, which is not only complicated in preparation process but also high in cost.

Republic of China Patent Publication No. 201808855 discloses a "manufacturing method of cemented material and mortar solidified material and mortar solidified material formed thereby". The manufacturing method includes: firstly providing a steel-making slag, and then the steel-making The slag is soaked in water to form an alkaline solution; then, the alkaline solution is separated from the steel-making slag, and the glass powder is added to the alkaline solution and stirred evenly to form a cementing solution; and finally cured The cementing solution is used to form a cementitious material; obviously, this manufacturing method also requires the addition of water or other solutions for mixing, and the addition of glass powder can be completed, so the manufacturing process is cumbersome.

According to the literature, the average production of 1 ton of pig iron produces about 300 kg of blast furnace stone, while the converter and electric arc furnace steelmaking, the average production of 1 ton of crude steel produces about 130 kg of converter ballast or 100-200 kg of electric arc furnace ballast. According to the statistics of the Ministry of Economy, the annual output of domestic electric arc furnace steel-making slag is 1 million tons (carbon steel and stainless steel slag). Whether the slag or reducing slag is residual iron or iron oxide, calcium oxide, silicon dioxide, Aluminum oxide, magnesium oxide and manganese oxide are the main components. The analysis shows that the chemical properties of the oxidized slag and reducing slag generated during steelmaking in the electric arc furnace are similar to those of cement and blast furnace stone powder, and they have properties similar to those of Bu Zuolan. The use of the above industrial waste as a cementing material for concrete is still the focus of research and development in related fields.

In addition, Taiwan’s construction industry uses about 20 million tons of cement every year, and the mainland area is as high as 800 million tons. However, in the process of manufacturing cement, high temperature kiln firing will emit a considerable amount of carbon dioxide, so under environmental protection measures To reduce kiln firing and make cement substitutes is also an urgent matter.

The main purpose of the present invention is to provide a method for manufacturing steel ballast cement, which refers to a method for making steel ballast cement by using oxidized ballast powder, reduced ballast powder and power plant fly ash in industrial waste, which can be used in normal temperature environment It is obtained by mixing in a dry way, without high-temperature firing, and without adding water during the mixing process, and can meet the requirements of cement setting time, compressive strength and dry shrinkage.

In order to achieve the above-mentioned implementation objective, the present invention provides a method for manufacturing steel ballast cementitious materials, which includes the following steps: (a) preparing oxidized ballast powder or a reduced ballast powder; and (b) at room temperature without water, Mix 0-70 wt% of oxidized ballast powder or reduced ballast powder with the remaining weight percentage of cement clinker or/and power plant fly ash to produce steel ballast cement; preferably, step (b) is Mix 30-60 wt% oxidized ballast powder and 20-70 wt% cement clinker and mix with the remaining weight percentage of power plant fly ash to produce oxidized steel ballast cement.

In one embodiment of the present invention, the oxidized ballast powder or reduced ballast powder is prepared by the following steps: (i) performing a magnetic separation, crushing and sieving process at least once; and (ii) performing a grinding and sieving process To produce oxidized ballast powder or reduced ballast powder.

In one embodiment of the present invention, step (b) is to mix 30-60 wt% reduced ballast powder and 20-70 wt% cement clinker with the remaining weight percentage of power plant fly ash to produce reduced Steel ballast cement material.

In one embodiment of the present invention, the ballast powder system includes at least compounds CaO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , MgO, Na ₂ O, MnO, CaCO ₃ and elements C, O, Si, Al , Fe, Ca, Mg, Mn, Ti, Na.

In one embodiment of the present invention, the reduced ballast powder system includes at least compounds CaO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , CaCO ₃ , MgO, SnO, Sb ₂ O ₃ , MnO and elements C, O, Si, Al, Fe, Ca, Mg, Mn, Sn, Sb.

In one embodiment of the present invention, the cement clinker system includes at least compounds SiO ₂ , CaO, Al ₂ O ₃ , Fe ₂ O ₃ , CaO, MgO, K ₂ O, Na ₂ O and elements Ca, Si, Al, Fe, Mg.

In one embodiment of the present invention, the fly ash system of a power plant includes at least compounds SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , CaO, MgO, K ₂ O, Na ₂ O and elements C, O, Si, Al, Fe, Ca, K, Mg, Na.

In an embodiment of the present invention, the steel ballast cement material is further prepared with a water-binder ratio of 0.2-0.3 to obtain a cement slurry.

In this way, the steel ballast cement material made of oxidized ballast powder, reduced ballast powder, power plant fly ash, etc. in industrial waste can indeed meet the requirements of cement setting time, compressive strength and dry shrinkage after testing. Requirements; overall, the manufacturing method of this case can reduce the cost of manufacturing steel ballast cement or cement, and can also achieve the purpose of resource recycling.

The purpose of the present invention and its structural and functional advantages will be explained based on the structure shown in the following drawings and in conjunction with specific embodiments, so that the reviewing committee can have a more in-depth and specific understanding of the present invention.

As shown in the first figure, a method for manufacturing steel ballast cement material of the present invention includes the following steps: (a) preparing oxidized ballast powder or reduced ballast powder; and (b) at normal temperature, reducing the weight percentage by 0- 70 wt% oxidized ballast powder or reduced ballast powder, mixed with the remaining weight percentage of cement clinker or/and power plant fly ash to produce steel ballast cement; preferably, the weight percentage of 30-60 wt% is oxidized The ballast powder or reduced ballast powder and 20-70 wt% cement clinker are mixed and mixed with the remaining weight percentage of power plant fly ash to prepare respectively oxidized steel ballast cement or reduced steel ballast cement.

The oxidized ballast powder or reduced ballast powder can be prepared, for example, by the following steps: (i) performing a magnetic separation, crushing and sieving procedure at least once; and (ii) performing a grinding and sieving (200#) procedure to The oxidized ballast powder or reduced ballast powder is obtained, as shown in the second figure.

In addition, through the following specific embodiments, the scope of the present invention can be further proved to be practical, but it is not intended to limit the scope of the present invention in any form.

Example 1: Preparation of steel ballast cement

The steel ballast cement material is formulated with the oxidized ballast and reduced ballast of Haiguang Iron and Steel and Longqing Iron and Steel. Since the source materials of the oxidized ballast and reduced ballast of Haiguang Steel and Longqing Iron and Steel are quite similar, the oxidized ballast powder used in the examples is used The mixture of Haiguang oxidized ballast 50% (wt) and Longqing oxidized ballast 50% (wt) was used for the experiment. Similarly, the reduced ballast powder was also used Haiguang reduced ballast 50% (wt) and Longqing reduced ballast 50% ( wt) to prepare the mixture.

Mix oxidized ballast powder (code O) and reduced ballast powder (code R) separately with cement clinker (code C) and F-class thermal power plant fly ash (code F) at different weight percentages at room temperature, mixing process There is no need to add water. After mixing, a total of 15 groups of oxidized ballast powder and 15 groups of reduced ballast powder are formed, as shown in Table 1.

Table I

The above cement clinker was purchased from a commercially available Taiwan cement, and X-ray diffraction analysis (XRD) was used to discuss the composition of each phase of the cement. The results are shown in the third figure, which shows that the main crystalline compounds of the cement are SiO ₂ and CaO , The secondary crystalline compounds are Al ₂ O ₃ , Fe ₂ O ₃ , CaO, MgO, K ₂ O, Na ₂ O, etc. The content of each element in the cement sample is discussed by X-ray fluorescence analysis (XRF). With the highest content of Ca, Si, Al, Fe, Mg and other elements, each compound obtained by XRD analysis is then gravimetrically calculated to calculate its chemical composition, and then the percentage of oxidation state content of each element of cement is calculated, as shown in Table 2. Then observe the crystal phase change with a scanning electron microscope (SEM). As shown in the third figure, the appearance of the cement is a needle-like CSH colloid (shown as a round frame in the figure) and a hexagonal piece of calcium hydroxide (as shown in the figure above) Box) combined.

Table II

The above-mentioned power plant fly ash was taken to Xingda Thermal Power Plant, and X-ray diffraction analysis (XRD) was used to discuss the composition products of each phase of the power plant fly ash. The results are shown in the fourth figure, which shows that the main crystalline compounds of the power plant fly ash are SiO ₂ , the secondary crystalline compounds are Al ₂ O ₃ , Fe ₂ O ₃ , CaO, MgO, K ₂ O, Na ₂ O, etc. Then, X-ray fluorescence analysis (XRF) is used to discuss each of the power plant fly ash samples Elemental content, in which C, O, Si, Al, Fe, Ca, K, Mg, Na and other elements have the highest content, and each compound obtained by XRD analysis is then gravimetrically calculated to calculate its chemical composition measurement, and then to estimate the power plant fly ash The percentage of the oxidation state content of the element is shown in Table 2. Scanning electron microscopy (SEM) was used to observe the crystalline phase change of the fly ash of the power plant. As shown in the fourth figure, the appearance of the fly ash of the power plant was staggered and combined with spherical structures of different sizes, and the particle size of the spherical particles was relatively large. There are pores of different sizes distributed in the middle (as shown in the box).

The oxidized ballast from Haiguang Iron and Steel Company was analyzed by X-ray diffraction analysis (XRD). The results are shown in the fifth figure. The figure shows that the main crystalline compounds of oxidized ballast of Haiguang Iron and Steel are CaO and SiO. _{2. The} secondary crystalline compounds are Al ₂ O ₃ , Fe ₂ O ₃ , MgO, Na ₂ O, MnO, CaCO ₃ and so on. Then, X-ray fluorescence analysis (XRF) is used to discuss the oxidized ballast samples of Haiguang Steel. Element content, in which C, O, Si, Al, Fe, Ca, Mg, Mn, Ti and other elements have the highest content, and various compounds obtained by XRD analysis are then gravimetrically calculated to calculate their chemical composition measurement, and then know their respective The percentage of the oxidation state content of the element is shown in Table 2. Scanning electron microscope (SEM) was used to observe the change of crystal phase. As shown in the fifth figure, the oxidized ballast of Haiguang Iron and Steel consisted of flaky, needle-like, angle-like, and needle-like CSH colloids (such as The round frame in the picture is pushed and stacked, and there are many pores of different sizes.

The oxidized ballast from Longqing Iron and Steel Company was analyzed by X-ray diffraction analysis (XRD). The results are shown in the sixth figure. The figure shows that the main crystalline compounds of oxidized ballast of Qingsteel are CaO, SiO ₂ , Fe ₂ O ₃ , the secondary crystalline compounds are Al ₂ O ₃ , MgO, CaCO ₃ , Na ₂ O, MnO, etc., then X-ray fluorescence analysis (XRF) to discuss the oxidation ballast samples of Longqing Steel The content of each element in the medium, of which C, O, Si, Al, Fe, Ca, Mg, Na, Mn and other elements have the highest content, and the various compounds obtained by XRD analysis are then gravimetrically calculated to calculate the chemical composition measurement, and then calculated The percentage of oxidation state content of each element is shown in Table 2. Scanning electron microscope (SEM) was used to observe the change of crystal phase. As shown in the sixth figure, the oxidized ballast of Longqing Iron & Steel consisted of plate-like, needle-like, angle-like, and needle-like CSH colloids with different particle sizes ( As shown in the figure, the round frame is pushed and stacked, and there are many pores of different sizes.

The reduction ballast from Haiguang Iron and Steel Co., Ltd. was analyzed by X-ray diffraction analysis (XRD). The results are shown in the seventh figure. The figure shows that the main crystalline compounds of the reduction ballast of Haiguang Iron and Steel are CaO and SiO. _{2. The} secondary crystalline compounds are Al ₂ O ₃ , Fe ₂ O ₃ , CaCO ₃ , MgO, SnO, Sb ₂ O ₃ , MnO, etc., then X-ray fluorescence analysis (XRF) to discuss the reduction ballast test of Haiguang Steel The content of each element in the sample, of which C, O, Si, Al, Fe, Ca, Mg, Mn, Sn, Sb and other elements have the highest content, and the various compounds obtained by XRD analysis are then gravimetrically calculated to calculate the chemical composition measurement. Knowing and further estimating the percentage of oxidation state content of each element of the reduced ballast of Haiguang Iron and Steel, as shown in Table 2. Scanning electron microscope (SEM) was used to observe the change of crystal phase. As shown in the seventh figure, the reduction ballast of Haiguang Iron and Steel consisted of flaky, needle-like, angular grain-like, and needle-like CSH colloids with different particle sizes (such as The round frame in the picture is pushed and stacked, and there are many pores of different sizes.

The reduction ballast from Longqing Iron and Steel Company will be used to understand the composition of each phase of the reduction ballast of Longqing Steel by X-ray diffraction analysis (XRD). The results are shown in the eighth figure. The crystalline compounds are CaO, SiO ₂ , the secondary crystalline compounds Al ₂ O ₃ , Fe ₂ O ₃ , CaCO ₃ , MgO, SnO, Sb ₂ O _3, etc. Then, the X-ray fluorescence analysis (XRF) is used to discuss the power plant flying The content of each element in the gray sample, of which C, O, Si, Al, Fe, Ca, Mg, Sn, Sb and other elements have the highest content, and the various compounds obtained by XRD analysis are then gravimetrically calculated to calculate the chemical composition measurement. It is known that the percentage of oxidation state content of each element is calculated as shown in Table 2. Scanning electron microscope (SEM) was used to observe the change of crystal phase. As shown in the eighth figure, the reduction ballast of Longqing Iron & Steel consisted of flaky, needle-like, angle-like, and needle-like CSH colloids with different particle sizes (such as The round frame in the picture is pushed and stacked, and there are many pores of different sizes.

In addition, the samples of oxidized ballast and reduced ballast are used to determine the harmful properties of heavy metals according to the analysis method of "leaching toxic business waste" in the "Hazardous Business Waste Certification Standard" (USEPA, 1992), and the toxic characteristic dissolution procedures used ( The experimental method of Toxicity Characteristic Leaching Procedure (TCLP) refers to the method of NIEA R201.12C of the Environmental Protection Agency, and the determination of the dissolution toxicity is based on the dissolution standard of the toxic business waste promulgated by the Environmental Protection Department of the Executive Yuan. According to the dissolution results, it is known that the detection value of each heavy metal is far lower than the control standard, there should be no problem of heavy metal pollution, and it can be classified as general business waste. Subsequent tests will be conducted using the above 30 groups of samples with different proportions of oxidized ballast powder or reduced ballast powder.

Example 2: Detecting the setting time

The cement material begins to hydrate after adding water. Due to the hydration process, CSH colloids are produced and strong 度 is obtained, which makes the internal structure more dense, and the oxidation check and reduction ballast are the conversion between liquid and solid state when condensed. And reduce the activity of ballast and produce hydration reaction, and the setting time is also one of the important indicators to evaluate the workability.

In order to analyze the influence of the blending amount of different cement pastes on the setting time, the measurement was carried out according to the ASTM C191 cement setting time test, and the mixing ratio and the water-binder ratio according to Table 1 were 0.2, 0.25, and 0.30, and cone-shaped cements were made respectively. Wood slurry, and measure the initial setting time and final setting time of cementitious material slurry with a Kelvin needle. The standard of discrimination is to penetrate the depth of the pure slurry sample surface with a Fischer needle, and there is a carved 度 ruler on the bracket of the Fischer tester, and there is a fixed lock of the Fischer needle next to the Fischer needle to the surface of the slurry. At the time, after releasing the fixed lock, then record the sink height at different times according to the 度 ruler. The initial settling time is 30 seconds and the settling height 度 is 25mm and the following, the time will be judged as the initial setting time, and the final settling time is that the settling height 度 cannot be generated on the slurry surface. For the test results, please refer to the ninth figure and the tenth Figure.

(1) Water-to-binder ratio of oxidized ballast cement material W/B=0.2, W/B=0.25, W/B=0.3

The test of setting time of hydraulic cement by Fischer needle is 1.5 to 3 hours for the initial setting time of cement and 3 to 6 hours for the final setting time. In detail, as shown in the ninth figure, when the water-to-binder ratio W/B=0.2, the setting time of C20F50O30, C30F40O30, C40F30O30 is 2 minutes for the initial setting and 11 minutes for the final setting. Compared with C100O00, the initial setting is 2 minutes and the final setting is 3 minutes. It is quite close to C10F50O40, C20F40O40, C30F30O40. The initial setting is 1, 22, 27 minutes, and the final setting is 33, 86, 94 minutes. The ratio of C100O00 is 2 minutes for the initial setting and 3 minutes for the final setting; the setting time for C00F50O50, C10F40O50, C20F30O50 is 25, 1, 105 minutes, and the final setting is 46, 22, and 155 minutes respectively. The value of the pure cement ratio C100O00 is 2 minutes for the initial setting and 3 minutes for the final setting; then according to the ratio of C70O30, C60O40, C50O50, C40O60, C00O100, and C100O00, the setting time of the initial setting is 1, 1, respectively 55, 78, 369, 2 minutes, and final setting are 3, 3, 78, 100, 448, and 3 minutes, respectively. Based on the reference value, the ratio of pure cement C100O00 is 2 minutes for initial setting and 3 minutes for final setting. It can be seen that the setting time of the oxidized ballast cement material increases with the increase of the amount of oxidized ballast, and the trend is quite obvious. When the water-binder ratio W/B=0.20, the ratio of C20F50O30, C30F40O30, C40F30O30, C70O30, C60O40, etc. is in line with cement. The setting time requirement is better.

When the water-binder ratio W/B=0.25, the setting time of C20F50O30, C30F40O30, C40F30O30 is 115, 103, 135 minutes, and the final setting is 124, 139, and 143 minutes, respectively. The setting time is 8 minutes and the final setting time is quite close to 90 minutes; for C10F50O40, C20F40O40, C30F30O40, the setting time is 84, 183, 159 minutes, the final setting is 115, 197, 211 minutes, and the reference value is pure cement ratio C100O00 The difference between the initial setting is 8 minutes and the final setting is 90 minutes; the setting time of C00F50O50, C10F40O50, C20F30O50 is 169, 131, 402 minutes, and the final setting is 485, 300, and 420 minutes, respectively. The ratio of C100O00 is 8 minutes for the initial setting and 90 minutes for the final setting; then for C70O30, C60O40, C50O50, C40O60, C00O100, C100O00, the initial setting time is 56, 86, 136, 165, 1084, 56 minutes respectively The final setting is 90, 136, 151, 189, 1445, and 77 minutes, respectively. Based on the reference value, the ratio of pure cement C100O00 is 8 minutes for the initial setting and 90 minutes for the final setting. It can be seen that the setting time of the oxidized ballast cement material increases with the increase of the amount of oxidized ballast. The trend is quite obvious. If the coagulated ballast is used for a longer time, it may take 1 whole day to mix in these 15 groups. In the ratio, the setting time of C70O30, C60O40, C50O50, C40O60 is closer to the reference value, and the ratio of pure cement is C100O00. Therefore, when the water-binder ratio W/B=0.25, it is better to use C20F50O30, C30F40O30, C40F30O30, C10F50O40, C70O30, C60O40, C50O50, C40O60, etc. to meet the cement setting time requirements.

When the water-binder ratio W/B=0.3, the setting time of C20F50O30, C30F40O30, C40F30O30 is 125, 169, 134 minutes, and the final setting is 212, 218, and 189 minutes, respectively. The setting time is 125 minutes, and the final setting is 170 minutes. The setting times of C10F50O40, C20F40O40, and C30F30O40 are 187, 208, and 117 minutes respectively, and the final setting is 231, 232, and 258 minutes. The initial setting is 125 minutes, and the final setting is 170 minutes, which is quite close; the setting time of C00F50O50, C10F40O50, C20F30O50 is 362, 111, 105 minutes, and the final setting is 373, 124, 127 minutes. Compared with C100O00, the initial setting is 125 minutes and the final setting is 170 minutes. The C70O30, C60O40, C50O50, C40O60, C00O100, C100O00 ratios, the initial setting time is 75, 83, 90, 152, 1232, 75 minutes, and final setting are 93, 95, 110, 164, 1632, and 93 minutes respectively. Based on the reference value, the ratio of pure cement C100O00 is 125 minutes for the initial setting and 170 minutes for the final setting. It can be seen that the setting time of the oxidized ballast cement material increases with the increase of the amount of oxidized ballast, and the trend is quite obvious. Among them, the setting time of C70O30, C60O40, C50O50, C40O60 is closer to the reference value, and the pure cement is C100O00. Therefore, when the water-to-binder ratio W/B=0.30, C20F50O30, C30F40O30, C40F30O30, C10F50O40, C20F40O40, C30F30O40, C10F40O50, C20F30O50, C70O30, C60O40, C50O50, C40O60, etc., the best setting time is to meet the cement setting requirements.

(2) Water-to-binder ratio of reduced ballast cement material W/B=0.2, W/B=0.25, W/B=0.3

The test of setting time of hydraulic cement by Fischer needle is 1.5 to 3 hours for the initial setting time of cement and 3 to 6 hours for the final setting time. In detail, as shown in the tenth figure, when the water-to-binder ratio W/B=0.2, the setting time of C20F50R30, C30F40R30, C40F30R30 is 3, 3, 3 minutes, and the final setting is 12, 9, 6 respectively. Minutes, according to the reference value, the ratio of pure cement C100R00 is 2 minutes for initial setting and 3 minutes for final setting; the setting time of C10F50R40, C20F40R40, C30F30R40 is 3, 3, 3 minutes, and the final setting is 15, 60, 7 minutes, according to the reference value, the ratio of pure cement C100R00 is 2 minutes for the initial setting and 3 minutes for the final setting; the setting time for C00F50R50, C10F40R50, C20F30R50 is 6, 10, 4 minutes, and the final setting is 11, 25, 7 minutes, according to the reference value of pure cement ratio C100R00, the initial setting is 2 minutes, and the final setting is 3 minutes, which is quite close; then, according to the ratio of C70R30, C60R40, C50R50, C40R60, C00R100, C100R00, the initial setting time Respectively: 130, 2, 4, 11, 10, 2 minutes, final setting: 180, 5, 6, 46, 220, 3 minutes, according to the reference value of pure cement ratio C100R00, initial setting is 2 minutes, final setting is 3 In minutes, the ratio of C70R30 and C00R100 is relatively large, and the rest of C60R40, C50R50 and C40R60 are relatively close to the reference value of pure cement C100O00, the trend is quite obvious. It can be seen that when the water-to-binder ratio W/B=0.20, C20F50R30, C30F40R30, C40F30R30, C10F50R40, C20F40R40, C30F30R40, C00F50R50, C10F40R50, C20F30R50, C60R40, C50R50, C40R60, etc.

When the water-binder ratio W/B=0.25, the setting time of C20F50R30, C30F40R30, C40F30R30 is 5, 7 and 4 minutes, and the final setting is 32, 51, and 16 minutes, respectively. The setting time is 8 minutes, and the final setting time is 90 minutes. The setting time of C10F50R40, C20F40R40, C30F30R40 is 6, 4, 4 minutes, and the final setting is 56, 50, and 18 minutes. The reference value is pure cement ratio C100R00 The difference between the initial setting is 8 minutes and the final setting is 90 minutes; the setting time of C00F50R50, C10F40R50, C20F30R50 is 6, 4 and 4 minutes respectively, and the final setting is 56, 50 and 18 minutes respectively. The ratio of the initial setting of C100R00 is 8 minutes, and the final setting is 90 minutes. There is a large gap between them; according to the ratio of C70R30, C60R40, C50R50, C40R60, C00R100, C100R00, the initial setting time is 60, 180, 160, 107 , 90, 8 minutes, and final setting are 116, 240, 190, 127, 252, and 90 minutes respectively. Based on the reference value, the ratio of pure cement ratio C100R00 is 8 minutes for initial setting and 90 minutes for final setting. It can be seen that the setting time of the reduced ballast cement material increases with the increase of the amount of reduced ballast, and the trend is quite obvious. Among them, the setting time of C70R30, C60R40, C50R50, C40R60 is closer to the reference value and the pure cement ratio C100R00. Therefore, when the water-binder ratio W/B = 0.25, it is better to use C70R30, C60R40, C50R50, C40R60 and other ratios to meet the setting time of cement.

When the water-binder ratio W/B=0.3, the setting time of C20F50R30, C30F40R30, C40F30R30 is 196, 153, 180 minutes, and the final setting is 300, 214, and 213 minutes, respectively. The setting time is 125 minutes and the final setting is 170 minutes. There is a large gap between C10F50R40, C20F40R40, and C30F30R40. The initial setting time is 565, 433, 371 minutes, and the final setting is 680, 570, and 540 minutes. The difference between C100O00 is 125 minutes for the initial setting and 170 minutes for the final setting; with C00F50R50, C10F40R50, and C20F30R50, the setting times are 540, 479, and 513 minutes, and the final setting is 656, 587, and 624 minutes respectively. The ratio of pure cement C100R00 is 125 minutes for the initial setting and 170 minutes for the final setting; in terms of the ratio of C70R30, C60R40, C50R50, C40R60, C00R100 and C100R00, the setting time is 180, 196 and 200 respectively , 170, 1, 125 minutes, and final setting are 240, 240, 250, 256, 14, 170 minutes, respectively. Based on the reference value, the ratio of pure cement C100R00 is 125 minutes for initial setting and 170 minutes for final setting. It can be seen that the setting time of the reduced ballast cement increases with the increase of the amount of reduced ballast, and the trend is quite obvious. It can be seen that the ratio of C70R30, C60R40, C50R50, and C40R60 is closer to the reference value, and the ratio of pure cement is C100R00. Therefore, when the water-binder ratio W/B=0.30, it is better to use C20F50R30, C30F40R30, C40F30R30, C70R30, C60R40, C50R50, C40R60, etc. to meet the cement setting time requirements.

In addition, according to the above analysis results, the coagulation time of the oxidized ballast cement material and the reduced ballast cement material is compared. When the water-to-binder ratio W/B=0.2, the initial setting time of C20F50O30, C30F40O30, C40F30O30 is 2 minutes, and the final setting is respectively 11 minutes; the setting time of C20F50R30, C30F40R30, C40F30R30 is 3, 3, 3 minutes, and the final setting is 12, 9, and 6 minutes, respectively. The setting time of the two cements is quite close; the rest of the ratio is mostly for reduction The setting time of ballast cement is shorter. When the water-to-binder ratio W/B=0.25, the initial setting time of C20F50O30, C30F40O30, C40F30O30 is 115, 103, 135 minutes, and the final setting time is 124, 139, 143 minutes; the initial setting time of C20F50R30, C30F40R30, C40F30R30 The coagulation was 5, 7, 4 minutes, and the final coagulation was 32, 51, and 16 minutes, respectively. Obviously, the coagulation time of the reduced ballast cement was shorter; the rest of the proportions were mostly the shorter coagulation time of the reduced ballast cement. When the water-to-binder ratio W/B=0.3, the setting time of C20F50O30, C30F40O30, C40F30O30 is 125, 169, 134 minutes, and the final setting is 212, 218, and 189 minutes; C20F50R30, C30F40R30, C40F30R30 has the initial setting time. The coagulation was 196, 153, 180 minutes, and the final coagulation was 300, 214, and 213 minutes, respectively. Obviously, the reduced ballast cement material has a longer setting time; the rest of the proportions are mostly based on the reduced ballast cement material.

Example 3: Detecting compressive strength 度

Compressive strength 度 is one of the most important indicators of general concrete and alkali cemented materials, mainly to understand the compactness and porosity of the sample. Set the water-binder ratio to 0.2, 0.25, and 0.30, and make a 5 cm × 5 cm × 5 cm cube sample, soak in saturated lime water, and conduct a compression test after 7 days, 28 days, and 56 days to discuss curing The relationship between time and compressive strength 度, please refer to Figure 11 and Figure 12 for test results.

(1) Water-to-binder ratio of oxidized ballast cement material W/B=0.2, W/B=0.25, W/B=0.3

In detail, as shown in the eleventh figure, when the water-to-binder ratio W/B=0.2, the C40F30O30, C30F40O30, and C20F50O30 were cured for 7 days, and their compressive strengths were 194.63, 243.23, and 190.24 kgf/cm ² , respectively, for 28 days Compressive strength 度 is 245.61, 296.05, 243.61 kgf/cm ^{2 respectively} , curing 56 days Compressive strength 度 is 250.81, 304.35, 250.29 kgf/cm ^{2 respectively} , according to the reference value pure cement ratio C100O00 curing 7 days, 28 days, 56 days The compressive strength 度 is 175.68, 185.95, and 343.28 kgf/cm ² , respectively, and the compressive strength 度 is quite close, and the compressive strength 度 with the C40F30O30 ratio is the highest. C30F30O40, C20F40O40, and C10F50O40 were treated for 7 days with compressive strength 度 of 215.67, 157.55, and 53.28 kgf/cm ^{2 respectively} , cured with 28 days of compressive strength 度 of 257.04, 216.15, 92.49 kgf/cm ² , and treated with 56 days of compressive strength 度 as 297.69, 223.35, 103.48 kgf/cm ² , according to the reference value pure cement ratio C100O00 curing 7 days, 28 days, 56 days compressive strength 度 is 175.68, 185.95, 343.28 kgf/cm ² compressive strength 度 differs greatly; C20F30O50, For C10F40O50 and C00F50O50, the 7-day compressive strength 度 is 147.33, 45.50, 4.46 kgf/cm ² , the 28-day compressive strength 度 is 204.63, 87.88, 5.33 kgf/cm ² , and the 56-day compressive strength 度 is 225.91, respectively. 100.56, 5.41 kgf/cm ² , the reference value of pure cement ratio C100O00 curing 7 days, 28 days, 56 days compressive strength 度 is 175.68, 185.95, 343.28 kgf/cm ² compressive strength 度 differs greatly. In terms of the ratio of C00O100, C40O60, C50O50, C60O40, C70O30, and C100O00, their 7-day curing pressure 度 is 1.60, 344.69, 446.73, 416.68, 570.51, 175.68 kgf/cm ² , and 28-day curing pressure 度 respectively It is 4.35, 349.73, 471.68, 439.52, 539.25, 185.95 kgf/cm ² , and the 56-day compressive strength 度 is 5.91, 418.21, 448.99, 518.83, 565.69, 343.28 kgf/cm ^{2 respectively} , according to the reference value pure cement ratio C100O00 curing The 7-day, 28-day, and 56-day compressive strengths 度 are 175.68, 185.95, and 343.28 kgf/cm ² compressive strengths 度 except C00O100, the rest of the ratios far exceed the reference values. The ratio of pure cement is quite different. It can be seen that the compressive strength of oxidized ballast cement 度 decreases with the increase of the amount of oxidized ballast, and the trend is quite obvious. When the water-to-binder ratio W/B=0.20, the C40F30O30, C30F40O30, C20F50O30, C30F30O40, C20F40O40, C10F50O40, C20F30O50, C40O60, C50O50, C60O40, C70O30 and other ratios are better to meet the requirements of the cement pressure resistance 度.

When the water-to-binder ratio W/B=0.25, the C40F30O30, C30F40O30, and C20F50O30 had 7-day compressive strength 度 of 223.68, 183.36, 114.31 kgf/cm ² , and 28-day compressive strength 度 of 276.84, 231.00, 189.00 kgf/ cm ² , curing 56-day compressive strength 度 is 296.67, 245.53, 202.05 kgf/cm ² , with reference to pure cement ratio C100O00 curing 7-day, 28-day, 56-day compressive strength 度 is 374.19, 443.00, 480.75 kgf/ cm ² , the compressive strength 度 differs greatly, among which C40F30O30 is still the strongest proportion 度; C30F30O40, C20F40O40, C10F50O40 have 7-day compressive strength 度 of 171.48, 116.76, 40.97 kgf/cm ² , and 28-day compressive strength 度 respectively It is 239.67, 179.67, 101.33 kgf/cm ² , curing 56 days compressive strength 度 is 244.11, 192.99, 103.12 kgf/cm ^{2 respectively} , according to the reference value pure cement ratio C100O00 curing 7 days, 28 days, 56 days compressive strength 度 respectively 175.68, 185.95, 343.28 kgf/cm ² compressive strength 度 differs greatly; C20F30O50, C10F40O50, C00F50O50 curing 7-day compressive strength 度 95.49, 13.47, 1.73 kgf/cm ^{2 respectively} , curing 28-day compressive strength 度 129.33, respectively , 48.00, 2.00 kgf/cm ² , curing 56 days compressive strength 度 is 152.25, 58.91, 1.73 kgf/cm ² , according to the reference value of pure cement ratio C100O00 curing 7 days, 28 days, 56 days compressive strength 度 is 175.68 , 185.95, 343.28 kgf/cm ² compressive strength 度 differs even more; in terms of the ratio of C00O100, C40O60, C50O50, C60O40, C70O30, C100O00, the 7-day compressive strength 度 of curing is 2.41, 279.32, 389.96, 471.64, respectively. 497.57, 374.19 kgf/cm ² , 28-day curing pressure 度 2.67, 318.92, 395.99, 445.67, 525.87, 443.00 kgf/cm ² , curing 56-day pressure 度 2.80, 366.04, 425.81, 503.51, 532.20, respectively 480.75 kgf/cm ² , according to the reference value pure cement ratio C100O00 curing 7 The compressive strength 度 of days, 28 days, and 56 days is 374.19, 443.00, and 480.75 kgf/cm ² respectively. The compressive strength 度 differs greatly. It can be seen that the compressive strength of oxidized ballast cement 度 decreases with the increase of the amount of oxidized ballast, and the trend is quite obvious. When the water-binder ratio W/B=0.25, it is better to use C50O50, C60O40, C70O30 and other ratios to meet the requirements of cement compressive strength 度.

When the water-to-binder ratio W/B=0.3, the C40F30O30, C30F40O30, and C20F50O30 had a 7-day curing pressure of 220.24, 172.20, and 109.72 kgf/cm ^{2 respectively} , and a 28-day curing pressure of 312.80, 240.77, and 161.97 kgf/ cm ² , curing 56-day compressive strength 度 is 308.28, 242.65, 181.43 kgf/cm ² , according to the reference value pure cement ratio C100O00 curing 7-day, 28-day, 56-day compressive strength 度 is 550.21, 608.36, 647.99 kgf/ cm ² , the compressive strength 度 differs greatly, among which C40F30O30 is still the strongest proportion 度; the C30F30O40, C20F40O40, C10F50O40 curing 7-day compressive strength 度 is 178.57, 94.20, 28.44 kgf/cm ² , and the 28-day compressive strength 度 respectively 285.95, 178.05, 72.48 kgf/cm ² , curing 56 days compressive strength 度 298.76, 179.63, 81.89 kgf/cm ^{2 respectively} , according to the reference value pure cement ratio C100O00 curing 7 days, 28 days, 56 days compressive strength 度 respectively 550.21, 608.36, 647.99 kgf/cm ² , the difference in compression strength 度 is quite large; C20F30O50, C10F40O50, C00F50O50 their curing 7-day compressive strength 度 is 87.24, 13.73, 1.45 kgf/cm ² , curing 28-day compressive strength 度 are 134.60, 46.772, 1.60 kgf/cm ² , curing 56 days compressive strength 度 is 150.24, 52.84, 1.60 kgf/cm ^{2 respectively} , according to the reference value pure cement ratio C100O00 curing 7 days, 28 days, 56 days compressive strength 度 are 550.21, 608.36, 647.99 kgf/cm ² , the difference in compressive strength 度 is larger; then C00O100, C40O60, C50O50, C60O40, C70O30, C100O00, the curing 7-day compressive strength 度 is 1.60, 217.59, 191.28, 371.71, 426.31, 550.21, respectively kgf/cm ² , the 28-day compressive strength 度 is 1.60, 240.75, 279.17, 402.91, 459.59, 608.36 kgf/cm ² , and the 56-day compressive strength 度 is 1.70, 264.85, 284.49, 418.75, 514.64, 647.99 kgf/ cm ² , cured with reference value pure cement ratio C100O00 for 7 days, 2 The 8-day and 56-day compressive strengths 度 are 550.21, 608.36, and 647.99 kgf/cm ² , respectively, and the compressive strengths 度 vary greatly. It can be seen that the compressive strength of oxidized ballast cement 度 decreases with the increase of the amount of oxidized ballast, and the trend is quite obvious. When the water-binder ratio W/B=0.30, it is better to use the ratio of C40O60, C50O50, C60O40, C70O30 and other compressive strength 度 closer to the requirement of cement.

(2) Water-to-binder ratio of reduced ballast cement material W/B=0.2, W/B=0.25, W/B=0.3

As shown in the twelfth figure, when the water-to-binder ratio W/B=0.2, the C40F30R30, C30F40R30, C20F50R30 curing pressure for 7 days 度 is 55.48, 45.01, 22.86 kgf/cm ^{2 respectively} , curing for 28 days compressive strength 度 respectively 70.25, 70.21, 28.25 kgf/cm ² , curing 56 days compressive strength 度 71.17, 77.29, 42.11 kgf/cm ^{2 respectively} , according to the reference value pure cement ratio C100R00 curing 7 days, 28 days, 56 days compressive strength 度 respectively It is 175.68, 185.952, 343.28 kgf/cm ² , and the compressive strength 度 is quite different, which can not meet the cement compressive strength 度 requirements; C30F30R40, C20F40R40, C10F50R40 whose curing 7-day compressive strength 度 is 54.10, 34.20, 10.41 kgf/cm ² , respectively The 28-day compressive strength 度 is 57.33, 53.49, 24.83 kgf/cm ² , and the 56-day compressive strength 度 is 63.55, 76.66, 28.75 kgf/cm ^{2 respectively} , and the reference value pure cement ratio C100R00 is cured for 7 days, 28 days The 56-day compressive strength 度 is 175.68, 185.95, and 343.28 kgf/cm ² respectively. The compressive strength 度 differs greatly and cannot meet the cement compressive strength 度 requirement; C20F30R50, C10F40R50, C00F50R50 are cured for 7 days. The compressive strength 度 is 31.52, 9.68, 1.73 kgf/cm ² , curing pressure for 28 days 度 is 61.84, 25.81, 6.02 kgf/cm ² , curing 56 days compression pressure 度 is 63.69, 37.49, 7.45 kgf/cm ^{2 respectively} , according to the reference value pure cement ratio C100R00 The 7-day, 28-day, and 56-day compressive strengths 度 are 175.68, 185.95, and 343.28 kgf/cm ² respectively. The compressive strength 度 differs greatly and cannot meet the cement compressive strength 度 requirements; C20F30R50, C10F40R50, and C00F50R50 are cured for 7 days compressive strength 度Respectively 31.52, 9.68, 1.73 kgf/cm ² , curing 28-day compressive strength 度 61.84, 25.81, 6.02 kgf/cm ² , curing 56-day compressive strength 度 63.69, 37.49, 7.45 kgf/cm ² , respectively, for reference The value of pure cement ratio C100R00 is 7 days, 28 days, and 56 days. The compressive strength 度 is 175.68, 185.95, and 343.28 kgf/cm ² respectively. The compressive strength 度 differs greatly, and the cement compressive strength 度 requirements cannot be met; then C00R100, C40R60 , C50R50, C60R40, C70R30, and C100R00, their 7-day curing pressures 度 are 1.77, 71.73, 106.80, 147.18, 171.84, 175.68 kgf/cm ² , 28-day curing pressures are 7.01, 189.24, 227.87, 254.06, 235.73, respectively , 185.95 kgf/cm ² , curing 56 days compressive strength 度 are 7.91, 265.98, 361.34, 311.40, 330.91, 343.28 kgf/cm ² , according to the reference value of pure cement ratio C100R00 curing 7 days, 28 days, 56 days of compression The strength 度 is 175.68, 185.95, and 343.28 kgf/cm ² , respectively. The compressive strength 度, except for the C00R100 ratio, far exceeds the reference value. The ratio of pure cement is quite different. It can be seen that the compressive strength of reduced ballast cement 度 decreases with the increase of the amount of reduced ballast, and the trend is quite obvious. When the water-binder ratio W/B=0.20, it is better to use C40R60, C50R50, C60R40, C70R30 and other ratios to meet the requirements of cement compressive strength 度.

When the water-to-binder ratio W/B=0.25, the C40F30R30, C30F40R30, C20F50R30 curing pressure for 7 days 度 is 171.53, 147.07, 70.16 kgf/cm ² respectively, and the curing pressure for 28 days 度 is 250.63, 177.65, 76.05 kgf/ cm ² , curing 56-day compressive strength 度 is 280.65, 216.97, 125.11 kgf/cm ² , according to the reference value pure cement ratio C100R00 curing 7-day, 28-day, 56-day compressive strength 度 is 177.20, 374.19, 480.75 kgf/ cm ² , the compressive strength 度 differs greatly and cannot meet the cement compressive strength 度 requirements; C30F30R40, C20F40R40, C10F50R40 curing 7-day compressive strength 度 114.03, 57.92, 17.37 kgf/cm ^{2 respectively} , and curing 28-day compressive strength 度 are 195.03, 176.07, 50.65 kgf/cm ² , curing 56 days compressive strength 度 is 199.81, 121.97, 53.01 kgf/cm ² , according to the reference value pure cement ratio C100R00 curing 7 days, 28 days, 56 days compressive strength 度 are 177.20, 374.19, 480.75 kgf/cm ² compressive strength 度 differs greatly, unable to meet the cement compressive strength 度 requirements; C20F30R50, C10F40R50, C00F50R50 its curing 7-day compressive strength 度 is 40.12, 14.1, 4.41 kgf/cm ² , curing 28 The daily compressive strength 度 is 86.93, 35.52 and 10.04 kgf/cm ^{2 respectively} , and the curing 56-day compressive strength 度 is 130.68, 42.05 and 11.23 kgf/cm ^{2 respectively} , and the reference value pure cement ratio C100R00 is cured for 7 days, 28 days and 56 The compressive strength of the day 度 is 177.20, 374.19, 480.75 kgf/cm ² respectively. The compressive strength 度 is quite different and cannot meet the compressive strength of the cement 度; then C00R100, C40R60, C50R50, C60R40, C70R30, C100R00 are cured for 7 days of compressive strength 度Respectively 4.35, 193.69, 256.75, 274.00, 458.57, 177.20 kgf/cm ² , 28-day curing pressure 度 8.75, 231.39, 301.52, 366.12, 484.29, 374.19 kgf/cm ^{2 respectively} , curing 56-day compression strength 度 are 10.92, 250.62, 330.36, 400.13, 494.23, 480.75 kgf/cm ² , according to the reference value pure cement ratio C100 R00 The compressive strengths 度 of 7 days, 28 days and 56 days were 177.20, 374.19 and 480.75 kgf/cm ² respectively. It can be seen that the compressive strength of reduced ballast cement 度 decreases with the increase of the amount of reduced ballast, and the trend is quite obvious. When the water-binder ratio W/B=0.25, it is better to use C40R60, C50R50, C60R40, C70R30 and other ratios close to the compressive strength of cement 度.

When the water-to-binder ratio W/B=0.3, the C40F30R30, C30F40R30, C20F50R30 curing pressure for 7 days 度 is 181.60, 126.04, 64.35 kgf/cm ² respectively, and the curing pressure for 28 days 度 is 284.04, 183.48, 142.56 kgf/ cm ² , curing compressive strength for 56 days 度 is 287.65, 210.00, 148.40 kgf/cm ² , according to the reference value pure cement ratio C100R00 curing compressive strength for 7 days, 28 days, 56 days 度 is 550.21, 608.36, 647.99 kgf/ cm ² , the compressive strength 度 differs greatly and cannot meet the cement compressive strength 度 requirements; C30F30R40, C20F40R40, C10F50R40 curing 7-day compressive strength 度 62.20, 74.92, 20.16 kgf/cm ^{2 respectively} , curing 28-day compressive strength 度 are 107.16, 141.23, 62.16 kgf/cm ² , 56-day curing pressure 度 is 199.84, 151.19, 67.89 kgf/cm ² , according to the reference value pure cement ratio C100R00 curing 7-day, 28-day, 56-day compression strength 度 are 550.21, 608.36, 647.99 kgf/cm ² compressive strength 度 is quite different and cannot meet the cement compressive strength 度 requirements; C20F30R50, C10F40R50, C00F50R50 its curing 7-day compressive strength 度 is 58.52, 16.13, 3.37 kgf/cm ² , curing 28 The daily compressive strength 度 is 122.12, 46.41 and 6.20 kgf/cm ^{2 respectively} , and the curing 56-day compressive strength 度 is 130.84, 64.65 and 13.24 kgf/cm ^{2 respectively} , and the reference value pure cement ratio C100R00 is cured for 7 days, 28 days, 56 The natural compressive strength 度 is 550.21, 608.36 and 647.99 kgf/cm ² respectively. The compressive strength 度 differs greatly and cannot meet the cement compressive strength 度 requirements; then the C00R100, C40R60, C50R50, C60R40, C70R30 and C100R00 ratios are used for curing The 7-day compressive strength 度 is 2.97, 218.87, 264.92, 396.04, 510.97, 550.21 kgf/cm ² , and the 28-day compressive strength 度 is 5.96, 243.11, 276.20, 447.91, 515.71, 647.99 kgf/cm ² , 56 days Compressive strength 度 is 9.35, 270.14, 274.28, 448.84, 541.74, 647.99 kgf/cm ² , according to the reference value pure cement Compared with C100R00, the 7-day, 28-day, and 56-day compressive strength 度 is 550.21, 608.36, and 647.99 kgf/cm ² compressive strength 度, which is quite different. It can be seen that the compressive strength of reduced ballast cement 度 decreases with the increase of the amount of reduced ballast, and the trend is quite obvious. When the water-binder ratio W/B=0.30, it is better to use C40R60, C50R50, C60R40, C70R30 and other ratios close to the compressive strength of cement 度.

In addition, according to the above analysis results, the compressive strength 度 of the oxidized ballast cement material and the reduced ballast cement material is compared. Obviously, the compressive strength 度 is higher with the oxidized ballast cement material. Analyze the resistance of the water cement ratio to the oxidized ballast cement material and the reduced ballast cement material The influence of the pressure 度 shows that the compressive strength 度 of the oxidized ballast cement material and the reduced ballast cement material decreases as the water-binder ratio increases.

Embodiment 4: Dry shrinkage detection

The dry shrinkage test can be used to understand the volume stability of the oxidized ballast cement material and the reduced ballast cement material. Therefore, a digital comparative length gauge is used to measure the change in the length of the sample shrinkage caused by the dehydration of the inorganic polymer. Generally, the smaller the shrinkage, the better. The following will discuss the volume stability of oxidized ballast cement and reduced ballast cement.

According to the test procedure of CNS 14603, the long 度 change test is carried out, the water-to-binder ratio is set to 0.2, 0.25 and 0.30, and the cement material slurry is poured into a rectangular column mold with a size of 285 mm × 25 mm × 25 mm. At the curing stage, the test body is demolded, and the initial value of the test body length 度 is measured after demolding. Afterwards, the dry shrinkage of each age is measured at 3 days, 7 days and 28 days of age. The amount of change 度 must be calibrated at the same position on the instrument before the test to verify the comparison of the zero length of the length gauge. It is mainly used to measure the change of the length 度 of the specimen of the cement paste bar. The formula for calculating the length of the sample 度 is as follows: ΔL _X =[(L ₂ -L ₁ )/G] ×100

Among them, ΔL _X : the length of the sample measured at age 度 change (%), L1: the reading of the initial length of the sample 度, minus the reference rod length at the same time 度 data value (mm), L2: the amount of the sample at age The reading of the relatively long 度, minus the reading (mm) of the par at the same age, G: the nominal effective gauge length of 250mm.

(1) Water/binder ratio of oxidized ballast cement material W/B=0.2

Please refer to the thirteenth graph, C40F30O30, C30F40O30, C20F50O30, their 7-day curing shrinkage rates are 0.057%, 0.032%, 0.24%, 28-day curing shrinkage rates are 0.057%, 0.047%, 0.301%, curing 56 days The dry shrinkage rates were 0.319%, 0.100%, and 0.351%, respectively. Based on the reference value, the pure cement ratio C100O00 cured for 7 days, 28 days, and 56 days. The dry shrinkage rates were 0.049%, 0.158%, and 0.161%, respectively. Among them, the ratio of C20F50O30 is higher; the shrinkage rate of C30F30O40, C20F40O40, and C10F50O40 is 7 days, and the shrinkage rate is 0.004%, 0.001%, and 0.035%, and the 28-day cure rate is 0.021%, 0.011%, and 0.046, respectively. %, 56-day curing shrinkage rate is 0.105%, 0.060%, 0.084%, compared with the reference value of pure cement ratio C100O00, the drying shrinkage rate is quite close; C20F30O50, C10F40O50, C00F50O50, curing 7-day drying shrinkage rate respectively 0.007%, 0.011%, -0.05%, 28-day curing shrinkage rates were 0.053%, 0.022%, -0.10%, 56-day curing shrinkage rates were 0.172%, 0.029%, -0.139%, based on reference value Compared with the ratio of pure cement C100O00, the dry shrinkage ratio is quite close; in terms of the ratio of C00O100, C40O60, C50O50, C60O40, C70O30, C100O00, the curing shrinkage ratio of 7 days is 0.082%, 0.242%, -0.007 respectively %, -0.004%, 0.021%, 0.049%, 28-day curing shrinkage rate is 0.097%, 0.376%, -0.014%, -0.018%, 0.035%, 0.158%, 56-day curing shrinkage rate is 0.115% , 0.376%, -0.025%, -0.039%, 0.091%, 0.161%, compared with the reference value pure cement ratio C100O00, except for the C00O100 ratio, the rest of the ratio dry shrinkage ratio is quite close to the reference value pure cement ratio. It can be seen that the shrinkage rate of oxidized ballast cement material increases with the increase of the amount of oxidized ballast, but the increase trend is not obvious. When the water-binder ratio W/B=0.20, it is better to use C40F30O30, C30F40O30, C30F30O40, C20F40O40, C10F50O40, C20F30O50, C40O60, C50O50, C60O40, C70O30, etc. to meet the requirements of cement shrinkage ratio.

(2) Water/binder ratio of oxidized ballast cement material W/B=0.25

Please refer to the fourteenth figure, C40F30O30, C30F40O30, C20F50O30 cure shrinkage rate of 0.018%, 0.014%, 0.118% for curing 7 days, 0.032%, 0.038%, 0.132% cure for 28 days, curing 56 days Dry shrinkage ratios are 0.070%, 0.049%, and 0.150%, respectively. Based on the reference value, the pure cement ratio C100O00 cures for 7 days, 28 days, and 56 days. The dry shrinkage ratios are -0.007%, -0.011%, and -0.018%, respectively. The rate is quite close, and the shrinkage rate is higher with the ratio of C20F50O30; C30F30O40, C20F40O40, C10F50O40 have 7-day curing shrinkage rates of 0.021%, 0.090%, and 0.011%, and 28-day curing shrinkage rates are 0.089% and 0.273, respectively. %, 0.039%, curing shrinkage rate of 56 days is 0.093%, 0.335%, 0.235%, compared with the reference value of pure cement ratio C100O00, the drying shrinkage rate is quite close, of which C20F40O40 ratio is higher; For C20F30O50, C10F40O50, C00F50O50, the 7-day curing shrinkage rates were 0.109%, 0.378%, and 0.144%, the 28-day curing shrinkage rates were 0.148%, 0.443%, and 0.395%, and the 56-day curing shrinkage rates were 0.176%, respectively. , 0.500%, 0.625%, compared with the reference value of pure cement ratio C100O00, the shrinkage rate of the three ratios is quite high and far exceeds the reference value; then with C00O100, C40O60, C50O50, C60O40, C70O30, C100O00 ratio, its The 7-day curing shrinkage rate was 0.148%, 0.206%, 0.001%, 0.079%, -0.154%, -0.007%, and the 28-day curing shrinkage rate was 0.219%, 0.282%, -0.004%, 0.036%,- 0.154%, -0.011%, curing shrinkage rate of 56 days is 0.317%, 0.340%, -0.079%, 0.068%, -0.210%, -0.018%, with the reference value of pure cement ratio C100O00 for comparison, except C00O100, In addition to the C40O600 ratio, the dry shrinkage of the other ratios is quite close to the reference value of pure cement. It can be seen that the shrinkage rate of oxidized ballast cement material increases with the increase of the amount of oxidized ballast, but the increase trend is not obvious. When the water-binder ratio W/B=0.25, it is better to use C40F30O30, C30F40O30, C30F30O40, C10F50O40, C20F30O50, C50O50, C60O40, C70O30, etc. to meet the requirements of cement dry shrinkage.

(3) Water-to-binder ratio of oxidized ballast cement material W/B=0.3

Please refer to the fifteenth figure, C40F30O30, C30F40O30, C20F50O30 cure shrinkage rate of 0.01%, 0.032%, 0.004% for 7 days, 0.029%, 0.050%, 0.018% cure for 28 days, 56 days cure The dry shrinkage ratios are 0.072%, 0.118%, and 0.025%, respectively, and the reference value of pure cement is C100O00 curing for 7 days, 28 days, and 56 days. The dry shrinkage ratios are -0.014%, -0.021%, and -0.07%, respectively. The rate is quite close to the reference value of pure cement ratio; C30F30O40, C20F40O40, C10F50O40 curing shrinkage rate of 7 days is 0.021%, 0.090%, 0.011%, 28 days curing shrinkage rate is 0.089%, 0.273%, 0.039%, The 56-day curing shrinkage rate of curing is 0.093%, 0.335%, 0.235% respectively, compared with the reference value pure cement ratio C100O00, in which the C20F40O40 ratio is higher, and the dry shrinkage ratio is quite close to the reference value pure cement ratio ; C20F30O50, C10F40O50, C00F50O50, the 7-day curing shrinkage rates were 0.021%, 0.107%, and 0.022%, the 28-day curing shrinkage rates were 0.13%, 0.221%, and 0.361%, and the 56-day curing shrinkage rates were 0.148, respectively. %, 0.251%, 0.435%, compared with the reference value of pure cement ratio C100O00, in which the shrinkage rate of C00F50O50 is higher, and the shrinkage rate is quite close to the reference value of pure cement ratio; then C00O100, C40O60, C50O50, For C60O40, C70O30, and C100O00, the 7-day curing shrinkage rate is -0.025%, 0.043%, 0.134%, 0.125%, -0.091%, -0.014%, and the 28-day curing shrinkage rate is -0.047, respectively. %, 0.126%, 0.191%, 0.132%, -0.112%, -0.021%, the curing shrinkage rate for 56 days is -0.06%, 0.16%, 0.154%, 0.197%, -0.137%, -0.07% The shrinkage is quite close to the reference value of pure cement. It can be seen that the shrinkage rate of oxidized ballast cement material increases with the increase of the amount of oxidized ballast, but the increase trend is not obvious. When the water-binder ratio W/B=0.30, it is better to use C40F30O30, C30F40O30, C20F50O30, C30F30O40, C10F50O40, C20F30O50, C10F40O50, C50O50, C60O40, C70O30, etc. to meet the requirements of cement shrinkage ratio.

(4) Water-to-binder ratio of reduced ballast cement material W/B=0.2

Please refer to the sixteenth figure, C40F30R30, C30F40R30, C20F50R30 curing shrinkage rate of 7 days is 0.054%, 0.028%, 0.018%, curing 28 days shrinkage rate is 0.077%, 0.032%, 0.028%, curing 56 days Dry shrinkage ratios are 0.077%, 0.067%, and 0.056%, respectively. Based on the reference value, pure cement ratio C100R00 is cured for 7 days, 28 days, and 56 days. The dry shrinkage ratios are 0.004%, 0.022%, and 0.032%, respectively. Reference value of pure cement ratio; C30F30R40, C20F40R40, C10F50R40 curing shrinkage rate of 0.046%, 0.007%, 0.257% for curing 7 days, 0.049%, 0.014%, 0.298% curing cure for 28 days, curing 56 days The dry shrinkage ratios are 0.07%, 0.147%, and 0.485% respectively, compared with the reference value pure cement ratio C100R00, in which the C10F50R40 ratio is higher, and the dry shrinkage ratio is quite close to the reference value pure cement ratio; C20F30R50 , C10F40R50, C00F50R50, the 7-day curing shrinkage rate were 0.039%, 0.137%, 0.328%, 28-day curing shrinkage rate were 0.079%, 0.259%, 0.382%, 56-day curing shrinkage rate were 0.179%, 0.431% and 0.435% are compared with the reference value pure cement ratio C100R00. Among them, the C10F40R50 and C00F50R50 ratios have higher shrinkage ratios. Only the ratio C20F30R50 dry shrinkage ratio is close to the reference value pure cement ratio. Based on the ratio of C00R100, C40R60, C50R50, C60R40, C70R30, and C100R00, the 7-day curing shrinkage rate is 0.082%, 0.285%, 0.032%, 0.104%, 0.011%, 0.004%, and the 28-day curing shrinkage The rates were 0.097%, 0.404%, 0.035%, 0.129%, 0.079%, and 0.022%, and the 56-day curing shrinkage rates were 0.12%, 0.52%, 0.053%, 0.133%, 0.147%, and 0.032%, respectively. For the comparison of pure cement ratio C100R00, except for the C40R60 ratio, the dry shrinkage ratio of the other ratios is quite close to the reference value pure cement ratio. It can be seen that the shrinkage rate of reduced ballast cement increases with the increase of the amount of reduced ballast, but the increase trend is not obvious. When the water-binder ratio W/B=0.20, it is better to use C40F30R30, C30F40R30, C20F50R30, C30F30R40, C20F40R40, C20F30R50, C50R50, C60R40, C70R30, etc. to meet the requirements of cement dry shrinkage.

(5) Water-to-binder ratio of reduced ballast cement material W/B=0.25

Please refer to the seventeenth figure, C40F30R30, C30F40R30, C20F50R30, their 7-day curing shrinkage rate is 0.004%, 0.029%, 0.022%, 28-day curing shrinkage rate is 0.039%, 0.072%, 0.061%, curing 56 days Dry shrinkage ratios are 0.047%, 0.104%, and 0.144%, respectively. Based on the reference value, the pure cement ratio C100R00 is cured for 7 days, 28 days, and 56 days. The dry shrinkage ratios are 0.004%, 0.022%, and 0.032%, respectively. The rate is quite close to the reference value of pure cement ratio; C30F30R40, C20F40R40, C10F50R40 curing shrinkage rate of 7 days is 0.032%, 0.072%, 0.114%, curing 28 days drying shrinkage rate is 0.046%, 0.100%, 0.157%, The 56-day curing shrinkage rate of curing is 0.089%, 0.107%, 0.222% respectively, compared with the reference value pure cement ratio C100R00, in which the C10F50R40 ratio is higher, and the dry shrinkage ratio is quite close to the reference value pure cement ratio Ratio; C20F30R50, C10F40R50, C00F50R50 ratio, the 7-day curing shrinkage rate was 0.018%, 0.103%, 0.119%, 28-day curing shrinkage rate was 0.035%, 0.231%, 0.463%, curing 56 days Dry shrinkage ratios are 0.049%, 0.483%, and 0.537%, respectively, compared with the reference value of pure cement ratio C100R00. Among them, C10F40R50 and C00F50R50 ratios have higher shrinkage ratios. Only the ratio C20F30R50 dry shrinkage ratios are close to the reference value. Cement ratio; then with C00R100, C40R60, C50R50, C60R40, C70R30, C100R00 ratio, its 7-day curing shrinkage rate is 0.148%, 0.333%, 0.0458%, 0.0408%, 0.077%, 0.05%, curing The 28-day shrinkage rates were 0.219%, 0.437%, 0.047%, 0.053%, 0.082%, and 0.062%, and the 56-day shrinkage rates were 0.32%, 0.54%, 0.052%, 0.066%, 0.085%, and 0.09%, respectively. Compared with the reference value pure cement ratio C100R00, except for the C00R100 and C40R60 ratios, the other ratio dry shrinkage ratios are quite close to the reference value pure cement ratio. It can be seen that the shrinkage rate of reduced ballast cement increases with the increase of the amount of reduced ballast, but the increase trend is not obvious. When the water-binder ratio W/B=0.25, it is better to use C40F30R30, C30F40R30, C20F50R30, C30F30R40, C20F40R40, C20F30R50, C50R50, C60R40, C70R30, etc. to meet the requirements of cement dry shrinkage.

(6) Water-to-binder ratio of reduced ballast cement material W/B=0.3

Please refer to the eighteenth figure, C40F30R30, C30F40R30, C20F50R30 cure shrinkage rate of 0.083%, 0.09%, 0.043% for 7 days, 0.219%, 0.129%, 0.057% cure for 28 days, 56 days cure The dry shrinkage ratios are 0.244%, 0.222%, 0.215%, respectively, and the reference value of pure cement is C100R00 curing for 7 days, 28 days, and 56 days. The dry shrinkage ratios are 0.003%, 0.014%, and 0.017%, respectively. The rate is high; for C30F30R40, C20F40R40, and C10F50R40, the 7-day curing shrinkage rates are 0.021%, 0.021%, and 0.097%, and the 28-day curing shrinkage rates are 0.046%, 0.057%, and 0.193%, respectively. The 56-day dry shrinkage ratios are 0.054%, 0.122%, and 0.204%, respectively, compared with the reference value pure cement ratio C100R00, in which the C10F50R40 ratio is higher, and the remaining ratio dry shrinkage ratios are quite close to the reference value pure cement. Mixing ratio; C20F30R50, C10F40R50, C00F50R50, the 7-day curing shrinkage rate is 0.021%, 0.021%, and 0.110%, the 28-day curing shrinkage rate is 0.056%, 0.042%, 0.466%, and the 56-day curing shrinkage rate, respectively It is 0.066%, 0.091%, 0.519%, compared with the reference value pure cement ratio C100R00, in which the dry shrinkage ratio of C00F50R50 ratio is higher, and the remaining ratio dry shrinkage ratio is quite close to the reference value pure cement ratio; then C00R100 , C40R60, C50R50, C60R40, C70R30, C100R00, the 7-day curing shrinkage rate is 0.025%, 0.247%, 0.031%, 0.018%, 0.04%, 0.003%, 28-day curing shrinkage rate is respectively 0.047%, 0.389%, 0.045%, 0.077%, 0.095%, 0.014%, curing shrinkage rate of 56 days is 0.06%, 0.55%, 0.108%, 0.116%, 0.112%, 0.017%, according to the reference value of pure cement Compared with C100R00, except for the C40R60 ratio, the rest of the ratio shrinkage ratio is quite close to the reference value of pure cement. It can be seen that the shrinkage rate of reduced ballast cement increases with the increase of the amount of reduced ballast, but the increase trend is not obvious. When the water-binder ratio W/B=0.30, it is better to use C30F30R40, C20F40R40, C20F30R50, C10F40R50, C50R50, C60R40, C70R30, etc. to meet the requirements of cement dry shrinkage.

Example 5: Crystal phase detection

The oxidized ballast cement material and the reduced ballast cement material slurry are made at the same water-to-binder ratio. The oxidized ballast cement material is 15 groups, and the reduced ballast cement material is 15 groups. The cast is made into a 5cm×5cm×5cm square sample, which is cured for 7 days. After the compression test at the curing age, sampling, drying, gold plating and other procedures are carried out, and a scanning electron microscope (SEM) is used to discuss the microstructure of the material, and the required test piece is taken out, and its size is about 3 -5mm, after 24 hours of evacuation and pre-treatment of carbon coating on the surface, place it under an electron microscope at 250 to 3000 times magnification, and observe the microcrystalline phase diagram of the test piece. The crystal phase diagrams of different ratios are shown in the eighteenth to twenty-third diagrams. On the crystal phase diagrams, you can see the appearance of needle-like CSH colloids (indicated by boxes), with different sizes of spherical structures Body (represented by a round frame).

In summary, the specific ratio defined by the ballast cement material in this case does have its special meaning and can achieve the specific effect.

It can be seen from the above implementation description that the present invention has the following advantages compared with the prior art:

1. The ballast cement material in this case was found through toxicity tests that the amount of toxic substances dissolved was far lower than the regulatory standards, so it did not have the toxicity of heavy metals and it was safe to use.

2. In this case, the ballast cement material can be mixed at room temperature without firing at high temperature, and it can be mixed in a dry manner in a non-aqueous environment, so the overall production process costs less and can be avoided Environmental pollution caused by high temperature firing.

3. This case uses oxidized ballast powder, reduced ballast powder, power plant fly ash, etc. in industrial waste to make steel ballast cement, and has been tested and confirmed to meet the requirements of cement setting time, compressive strength and dry shrinkage, so it can be To achieve the purpose of resource recovery and reuse.

In summary, the manufacturing method of the steel ballast cement material of the present invention can indeed achieve the expected use effect through the embodiments disclosed above, and the present invention has not been disclosed before the application, and it has fully complied with the patent law Regulations and requirements. I filed an application for a patent for invention in accordance with the law, pleaded for the review, and granted the patent.

However, the illustrations and descriptions disclosed above are only preferred embodiments of the present invention, and are not intended to limit the scope of protection of the present invention; those who are familiar with this skill, according to the characteristic scope of the present invention, do other things Equivalent changes or modifications should be regarded as not departing from the design scope of the present invention.

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Figure 1: The flow chart of the steps of the preferred embodiment of the present invention.

The second figure: the preparation flow chart of the oxidized ballast powder or the reduced ballast powder in the preferred embodiment of the present invention.

Third figure: X-ray diffraction analysis (XRD) diagram and scanning electron microscope (SEM) crystal phase diagram of cement clinker.

Fourth figure: X-ray diffraction analysis (XRD) diagram and scanning electron microscope (SEM) crystal phase diagram of power plant fly ash.

Fifth picture: X-ray diffraction analysis (XRD) picture and scanning electron microscope (SEM) crystal phase picture of ballast oxide (sea light).

Figure 6: X-ray diffraction analysis (XRD) diagram and scanning electron microscope (SEM) crystal phase diagram of the ballast oxide (Longqing).

Figure 7: X-ray diffraction analysis (XRD) diagram and scanning electron microscope (SEM) crystal phase diagram of reduced ballast (sea light).

Figure 8: X-ray diffraction analysis (XRD) diagram and scanning electron microscope (SEM) phase diagram of reduced ballast (Longqing).

The ninth figure: the analysis chart of the blending amount and setting time of oxidized ballast cement materials with different water-binder ratios.

Figure 10: Analysis chart of blending amount and setting time of reduced ballast cement materials with different water-binder ratios.

Figure 11: Analysis chart of blending amount and compressive strength of oxidized ballast cement materials with different water-binder ratios.

Figure 12: Analysis chart of the blending amount and compression strength of reduced ballast cement materials with different water-binder ratios.

Figure 13: Analysis chart of blending amount and dry shrinkage of oxidized ballast cement material with water-binder ratio of 0.2.

Figure 14: Analysis chart of blending amount and dry shrinkage of oxidized ballast cement material with water-binder ratio of 0.25.

Figure 15: Analysis chart of blending amount and dry shrinkage of oxidized ballast cement material with water-binder ratio of 0.3.

Figure 16: Analysis chart of blending amount and dry shrinkage of reduced ballast cement material with water-binder ratio of 0.2.

Figure 17: Analysis chart of blending amount and shrinkage rate of reduced ballast cement material with water-binder ratio of 0.25.

Figure 18: Analysis chart of blending amount and dry shrinkage of reduced ballast cement material with water-binder ratio of 0.3.

Figure 19: Scanning electron microscope (SEM) phase diagram of different oxidized ballast cement C40-F30-O30 (1);

Figure 20: Scanning electron microscope (SEM) crystal phase diagram of different ballast cement materials (2)

Figure 21: Scanning electron microscope (SEM) phase diagram of different oxidized ballast cement material and reduced ballast cement material (3);

Figure 22: Scanning electron microscope (SEM) phase diagram of different reduced ballast cement materials (4);

Figure 23: Scanning electron microscope (SEM) phase diagram of different reduced ballast cement materials (5).

Claims (9)

A method for manufacturing steel ballast cement material, comprising the following steps: 　　 (a) prepare oxidized ballast powder or a reduced ballast powder; and (b) at room temperature, change the weight percentage of 0-70 wt% of the oxidized ballast powder or the The reduced ballast powder is mixed with the remaining weight percentage of cement clinker or/and power plant fly ash to produce steel ballast cement. The method for manufacturing steel ballast cement as described in item 1 of the patent application scope, wherein the oxidized ballast powder or the reduced ballast powder is prepared by the following steps: (i) performing a magnetic separation, crushing and sieving process at least once ; And (ii) performing a grinding and sieving (200#) procedure to prepare the oxidized ballast powder or the reduced ballast powder. The method for manufacturing steel ballast cement as described in item 1 of the patent scope, wherein the step (b) is to mix 30-60 wt% of the oxidized ballast powder and 20-70 wt% of the cement clinker with The remaining weight percentages of the power plant fly ash are mixed to produce oxide steel ballast cement. The method for manufacturing steel ballast cement as described in item 1 of the patent scope, wherein the step (b) is to mix 30-60 wt% of the reduced ballast powder and 20-70 wt% of the cement clinker with The remaining weight percentage of the power plant fly ash is mixed to produce reduced steel ballast cement. The method for manufacturing steel ballast cement as described in item 1 or 2 of the patent application scope, wherein the ballast powder includes at least compounds CaO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , MgO, Na ₂ O, MnO, CaCO ₃ and elements C, O, Si, Al, Fe, Ca, Mg, Mn, Ti, Na. The method for manufacturing steel ballast cement as described in item 1 or 2 of the patent application scope, wherein the reduced ballast powder includes at least compounds CaO, SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , CaCO ₃ , MgO, SnO , Sb ₂ O ₃ , MnO and elements C, O, Si, Al, Fe, Ca, Mg, Mn, Sn, Sb. The method for manufacturing steel ballast cement as described in item 1 or 2 of the patent application scope, wherein the cement clinker includes at least compounds SiO ₂ , CaO, Al ₂ O ₃ , Fe ₂ O ₃ , CaO, MgO, K ₂ O, Na ₂ O and elements Ca, Si, Al, Fe, Mg. The method for manufacturing steel ballast cement as described in item 1 or 2 of the patent application scope, wherein the fly ash of the power plant includes at least compounds SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , CaO, MgO, K ₂ O, Na ₂ O and elements C, O, Si, Al, Fe, Ca, K, Mg, Na. The method for manufacturing steel ballast cement as described in item 1 or 2 of the patent application scope, wherein the steel ballast cement is further prepared with a water-binder ratio of 0.2-0.3 to obtain a cement slurry.

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