CN113200727A - Method for improving rheological property of PVA fiber and nano-silica cement-based composite material - Google Patents
Method for improving rheological property of PVA fiber and nano-silica cement-based composite material Download PDFInfo
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- CN113200727A CN113200727A CN202110701791.0A CN202110701791A CN113200727A CN 113200727 A CN113200727 A CN 113200727A CN 202110701791 A CN202110701791 A CN 202110701791A CN 113200727 A CN113200727 A CN 113200727A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention discloses a method for improving the rheological property of a PVA fiber and nano-silica cement-based composite material, belonging to the technical field of cement preparation, wherein the improvement method comprises the steps of adding the PVA fiber with the length-diameter ratio of 100-300, and improving the PVA fiber and nano-SiO by adjusting the length-diameter ratio of the PVA fiber2The cement-based composite material has rheological property, can effectively improve the cement strength, has the functions of adsorption, air entraining, dispersion, wetting and solubilization, can maximally improve the use efficiency of cement, and ensures good cement fluidity.
Description
Technical Field
The invention relates to the technical field of cement preparation, in particular to a method for improving the rheological property of a PVA fiber and nano-silica cement-based composite material.
Background
In order to improve the ductility and toughness of traditional cement-based materials and to improve their mechanical properties and durability, the addition of fibers is one of the most effective methods. A new type of building material, which is formed by using a cement-based material as a matrix and by uniformly dispersing discontinuous fibers in the matrix, is called Fiber Reinforced cement-based Composites (FRCC). At present, the most commonly used fibers in engineering mainly include steel fibers, Polyvinyl Alcohol fibers (PVA), basalt fibers, carbon fibers, polypropylene fibers, glass fibers, and the like. Among them, the PVA fibers have good dispersibility, can be uniformly distributed in cement-based materials, and have excellent characteristics such as high strength, high elastic modulus, no toxicity, good hydrophilicity, and excellent acid and alkali resistance, and thus are often used as reinforcing materials to prepare fiber-reinforced cement-based composite materials (PVA fiber-reinforced cement-based composite materials, abbreviated as PVA-FRCC). Previous researches show that the PVA-FRCC has high compressive strength, ductility and toughness and excellent durability. Meanwhile, the PVA-FRCC can meet the requirements of large span, light weight and long service life of a building structure, can greatly prolong the service life of the structure and reduce the maintenance cost of the structure in the service period when used as a structural material of a hydraulic building, and can realize reasonable utilization of resources and protect the ecological environment.
Due to the characteristics of small particle size, large specific surface area and the like, the nano material has special effects such as macroscopic quantum tunneling effect, surface effect, small-size effect and the like, and the excellent characteristics of the nano material make the nano material popular with numerous scholars and engineers in the aspect of building engineering materials and show bright development prospects. The nanoparticles commonly used today to improve the properties of cement-based composites consist mainly of nano-SiO2TiO 2 nanoparticles2Nano Fe2O3And nano CaCO3And the like. Nano-SiO in contrast to other particles2Not only can play a filling role, but also can play a filling role2Incorporation into waterAfter the mud-based composite material is used, the cement can react with Ca (OH) in the cement2The reaction generates calcium silicate hydrate gel (C-S-H), and the reaction of the calcium silicate hydrate gel and the C-S-H is an exothermic reaction, so that the hydration reaction is further accelerated. In addition, the nano SiO2The C-S-H gel can play a role of a crystal nucleus in a matrix, and is bonded on the surface of the C-S-H gel to form a three-dimensional network structure, so that the microstructure of the cement-based material is obviously improved, and the mechanical strength and the durability of the cement-based material are improved. Thus the nano SiO2The addition to cement-based composites has become one of the important means to improve the performance of building materials.
Although, PVA fiber and nano SiO were added2Can play the roles of bridging cracks and transferring load in the cement-based material, so that PVA fiber and nano SiO are added2Compared with the traditional cement-based material, the cement-based material has higher ductility, toughness and bending strength. However, in order to pursue the ultra-high mechanical properties of fiber cement-based materials, the fiber blending amount is gradually increased in recent years, and the fiber blending mode is different, and these behaviors cause that the fibers cannot be uniformly dispersed in the matrix, the rheological property is poor, the mixture forming is difficult, and the application of the fiber cement-based composite material is limited, therefore, the need for providing a method for improving the PVA fibers and the nano SiO is needed2A method for rheological properties of a cement-based composite material.
Disclosure of Invention
The invention aims to provide a method for improving PVA fiber and nano SiO2A method for rheological properties of a cement-based composite material.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a method for improving the rheological property of a PVA fiber and nano-silica cement-based composite material, wherein the PVA fiber with the length-diameter ratio of 100-300 is added.
Preferably, PVA fibers with the length-diameter ratio of 200-300 are added.
Preferably, the volume mixing amount of the PVA fiber is 0.3-1%.
Preferably, the volume mixing amount of the PVA fiber is 0.3-0.8%.
Preferably, the volume mixing amount of the PVA fiber is 0.3-0.5%.
PVA fiber and nano SiO2The yield stress and plastic viscosity of the cement-based composite material are increased along with the increase of the length-diameter ratio of the fiber, and the flow expansion degree is opposite to the flow rate. The influence of different shapes of particles on the plastic viscosity of the slurry is as follows: needle bar > lamellar > cube/grain > spherical. The PVA fiber is typically needle-rod-shaped particles and is easy to overlap with each other in a suspension containing uniform spherical particles, the larger the length-to-diameter ratio is, the larger the probability and the number of winding into a net-shaped structure are, and the net-shaped structure provides a blocking force opposite to the flowing direction of the slurry in the flowing process of the slurry, so the macroscopic expression is that the plastic viscosity of the slurry is increased and the flowing speed is reduced. In addition, the study according to the particle surface water layer thickness (WFT) model shows that the PVA fiber and the nano SiO2The yield stress and the plastic viscosity of the cement-based composite material and the WFT are in an exponential function relationship, and the PVA fiber and the nano SiO form an exponential function with the gradual increase of the thickness of the water layer among particles2The plastic viscosity and yield stress of the cement-based composite material are obviously reduced, the flow rate and flow expansion degree are linearly related to WFT, the flow rate and flow expansion degree of slurry are increased along with the increase of the thickness of a water layer between particles, and PVA fibers and nano SiO2In the cement-based composite material, the specific surface area of the fiber with larger length-diameter ratio and length of the fiber is larger, so that free water in the fiber is easily absorbed, the moisture of the wrapped particles is reduced, the thickness of water films among particles is reduced, the friction among particles lacking free water lubrication is increased, the main force required to be overcome when slurry flows is increased, the yield stress is increased, and the flow expansion degree is reduced. Therefore, the length-diameter ratio of the PVA fiber is limited to 100-300.
When the doping amount of the PVA fiber is only increased, the PVA fiber and the nano SiO2The flow spread and flow rate of the cement-based composite material decreases while the yield stress plastic viscosity increases. The reason is that under the premise of constant water-cement ratio, the free water amount in the mixture is also constant, and the fiber mixing amount is increased, so that the free water is not enough to wet the surfaces of solid particles, and the friction among the particles is increased. In addition, after the fiber content is increased, the fiber is suspendedThe concentration of solid particles in the floating phase is increased, the particles are easy to mutually collide to generate extra energy loss, and the PVA fiber and the nano SiO under the combined action of the two2The cement-based composite material has poor fluidity and increased rheological parameters. However, the rheological parameter is not infinitely increased, a critical value exists in the fiber mixing amount, and the change of the rheological parameter of the mixture after the critical value is exceeded tends to be smooth until the flow of the mixture is stopped. This may be due to the critical loading of the fibers that agglomerate or clump, impeding the flow of the blend. In addition, the critical doping amount decreases with increasing aspect ratio. After the PVA fiber is added, a flocculation structure in the composite material is broken and recombined under the shearing action, so that the increment of a certain rheological parameter is sharply reduced, and the strain hardening phenomenon can also occur under the conditions of certain fiber mixing amount and good fiber dispersion.
The introduction of the fiber increases the number of interface defects, the bonding force of the boundary is weakened due to the enrichment of free water, and the pores left after the water evaporation can weaken the PVA fiber and the nano SiO2The strength of the cement-based composite material and therefore the optimization of the interfacial zone is very important. The mixed material with volcanic ash activity has the characteristic of small diameter (micron-scale and nanometer-scale), and can fill the pores in the interfacial region and perform secondary hydration reaction to improve the PVA fiber and the nanometer SiO2The interface bonding force and the strength of the cement-based composite material. The mixed material also has the characteristic of particles with large specific surface area, the concentration of solid particles is obviously increased after the mixed material is added into slurry, and free water released by filling pores is not enough to wet the surfaces of the particles, so that PVA fibers and nano SiO are caused2The flow parameter of the cement-based composite material is reduced, and the segregation resistance is improved. Therefore, the volume mixing amount of the PVA fiber is limited to 0.3 to 1 percent, and the nano SiO2The addition amount of (A) is 3-5 parts.
Preferably, the method further comprises adding a mixed material, wherein the mixed material comprises copper slag, gypsum, volcanic ash, metakaolin and fly ash. Preferably, 200-300 parts of copper slag, 40-80 parts of gypsum, 30-60 parts of volcanic ash, 50-100 parts of metakaolin and 150-200 parts of fly ash are added.
The rheological property of the mixed material is influenced to a certain extent after the mixed material is added, but the influence degree of different mixed materials on the water requirement and the setting time of the standard consistency is different. The addition of copper slag slightly increases the water requirement of the standard consistency of cement, prolongs the setting time and slightly reduces the fluidity of mortar. The addition of metakaolin and gypsum reduces the water demand of cement, prolongs the initial and final setting time and increases the fluidity of mortar. This is because metakaolin has very low activity or substantially no activity, and the addition of metakaolin relatively reduces the amount of cement clinker, and although hydration can occur, the amount of hydration products produced is reduced, whereas gypsum, which is a filler mixture, does not substantially participate in the hydration reaction, and its addition reduces the clinker content in the cement, so that the amount of products produced by cement hydration is reduced, thus causing an increase in setting time, and at the same time, the gypsum particles, which are not water-absorbing on the surface, fill the voids of the flocculation structure and release free water, so that its addition reduces the water requirement for the standard consistency of the cement. After the volcanic ash and the fly ash are added, the water requirement of the standard consistency of the cement is increased, the initial and final setting time is shortened, and the fluidity of the mortar is reduced. The two mixed materials have certain pozzolanic activity, more importantly, the two mixed materials belong to porous substances with loose structures, have large specific surface areas and are easy to absorb water, the water filled between cement particles is absorbed by the mixed materials, the water demand is inevitably increased, and the addition of the materials with large specific surface areas accelerates the hydration of cement, increases the amount of cement hydration products, and shortens the initial setting time.
The mixing of different mixed materials has great influence on the net slurry penetration degree of cement, the addition of active substances such as copper slag, fly ash and the like improves the hydration rate of the cement, the amount of hydration products is increased, so that the net slurry penetration degree of the cement is reduced at the same time, wherein the reduction amount of the net slurry penetration degree of the fly ash is the largest, which also shows that the activity of the fly ash is obviously higher than that of other mixed materials. The addition of metakaolin and gypsum reduces the relative content of clinker in cement, greatly delays the hydration of cement paste, reduces the amount of products such as hydrated calcium silicate and the like generated in the early stage of cement hydration, and thus the reduction of the penetration of the paste is lower, which also indicates that the metakaolin and the gypsum have basically no activity or very low activity.
The type and the mixing amount of the mixed materials have great influence on the rheological property of the cement paste. The addition of the mixed materials of copper slag, fly ash, metakaolin and the like can increase the water requirement of the standard consistency of cement, shorten the setting time and reduce the fluidity of mortar, so that the yield value and the plastic viscosity of cement paste are increased to a certain extent, and the effect is enhanced along with the increase of the addition amount, so that the kiln ash activated coal gangue is particularly obvious; the addition of gypsum and metakaolin can improve the fluidity of the cement and delay the setting, and the more the addition amount is, the stronger the delay effect is.
Preferably, the method for improving the rheological property of the PVA fiber and nano-silica cement-based composite material specifically comprises the following steps:
s1, mixing cement and a mixed material, adding 1/2 water, and pre-mixing for 20-30 s to obtain mortar;
s2, mixing the nano SiO2Mixing the particles with a water reducing agent, adding the mixture into the residual water, stirring and dispersing, adding the mixture into the mortar after the mixture is uniformly dispersed, and stirring for 1-2 min to obtain a mixed material;
and S3, adding PVA fibers into the mixture obtained in the S2, and uniformly stirring.
The invention discloses the following technical effects:
3D printing requires that the material has rapid formability, can stand immediately after flowing out of a printer, and can not flow any more, namely, the material has excellent thixotropic property (higher plastic viscosity, lower ultimate shear stress, rapid rheology after stirring, and rapid standing once flowing out), and simultaneously has faster setting time and higher early strength. Otherwise the printed structure dimensions deviate significantly from the original design and the lower part cannot be deformed during the continuous lamination process. The invention improves the PVA fiber and the nano SiO by adjusting the length-diameter ratio of the PVA fiber2The cement-based composite material has rheological property, can effectively improve the cement strength, has the functions of adsorption, air entraining, dispersion, wetting and solubilization, can maximally improve the use efficiency of cement, ensures good cement fluidity, and can be used for 3And D, printing.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The cement in the embodiment of the invention is P.O42.5 type ordinary portland cement produced by New-village Meng-electrician group in HenanThe degree is 3160kg/m3The technical indexes refer to the national standard GB 175-2007. The grade I fly ash produced by Luoyang power plant is used as tap water supplied by Zhengzhou city. High-strength and high-modulus polyvinyl alcohol fibers (PVA fibers) produced by the company of Collybia, Japan are selected. Selecting nanometer SiO produced by Hangzhou Wanjing new material limited company2The appearance of the water reducing agent is white powder, the water reducing agent is a polycarboxylic acid high-performance water reducing agent which is a light yellow liquid, and the water reducing rate is 25%.
The method for improving the rheological property of the PVA fiber and nano-silica cement-based composite material specifically comprises the following steps:
s1, mixing cement and a mixed material, adding 1/2 mass of water, and pre-mixing for 25s to obtain mortar;
s2, mixing the nano SiO2Mixing the particles with a water reducing agent, adding the mixture into the residual water, stirring and dispersing the mixture, adding the mixture into the mortar after the mixture is uniformly dispersed, and stirring the mixture for 2min to obtain a mixed material;
and S3, adding PVA fibers into the mixture obtained in the S2, and uniformly stirring.
Examples 1 to 9 all adopt the above steps to prepare PVA fibers and nano silica cement-based composite materials, and the difference is that the mixture ratio of the added raw materials is different, wherein the aspect ratio of the PVA fibers of examples 1 to 2 is 100, the aspect ratio of the PVA fibers of examples 3 to 4 is 200, the aspect ratio of the PVA fibers of examples 5 to 6 is 300, and the aspect ratio of the PVA fibers of examples 7 to 9 is 230, as shown in table 1:
TABLE 1
Comparative example 1
The only difference from example 7 is that the aspect ratio of the PVA fiber is 400.
Comparative example 2
The only difference from example 7 is that the aspect ratio of the PVA fiber is 75.
Comparative example 3
The difference from example 7 is only that the volume content of the PVA fiber is 3%.
Comparative example 4
The difference from example 1 is only that the preparation method is as follows:
s1, mixing cement and a mixed material, adding 1/2 water, and pre-mixing for 25s to obtain mortar;
s2, mixing the nano SiO2And mixing the particles, the PVA fiber and the water reducing agent, adding the mixture into the residual water, stirring and dispersing, adding the mixture into the mortar after the mixture is uniformly dispersed, and stirring for 2 min.
The cement-based composite materials prepared in the examples and the comparative examples were subjected to a micro-slump test, a fluidity test and a 1-day compressive and flexural strength test, respectively, according to the national standards of Standard methods for testing the Properties of general concrete admixtures (GB/T50080-2016), the method for testing the fluidity of Cement mortar (GB/T2419-2005) and the Standard of methods for testing the Properties of general concrete admixtures (GB/T50080-2002). The test results are shown in Table 2.
TABLE 2
As can be seen from table 2, the composite material of the present invention has good fluidity, and meets the requirements of 3D printing.
The rheological property is tested by adopting a TR-CRI type full-automatic concrete rheometer produced by Shanghai concrete Rui instruments and Equipment Co., Ltd, and the specific test method is as follows:
(1) and (3) loading a testing barrel with the inner diameter of 300mm and the height of 310mm into 2/3 volume of fresh cement-based composite material, installing a cross rotor, controlling the testing barrel to ascend until the testing barrel is immersed to the position of 150mm of the rotor, testing the torque at the rotating speed of 0.1(rps), and calculating to obtain the static yield stress.
(2) After the static test is finished, the immersion depth of the cross rotor is kept unchanged, the torque generated when the rotating speed is 0.6, 0.55, 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2 and 0.15(rps) is tested in sequence is tested, and the dynamic yield stress and the plastic viscosity of the freshly mixed cement-based composite material are calculated. Due to the complexity of the impeller rotation, the shear stress and shear rate are calculated using the measured torque and impeller speed, as follows:
T＝G+H×N
in the formula: t-torque, in Newton-meters (N.m);
g is the intercept between the extension line of the linear section of the curve and the y axis;
h-the slope of the linear segment of the curve;
n-impeller speed in revolutions per second (rps).
(3) And (3) changing the cross rotor, installing a cylindrical rotor (phi 200x200mm), controlling the test barrel to ascend until the cylindrical rotor is immersed for 150mm, sequentially testing the torque generated when the rotating speed is 0.6, 0.55, 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2 and 0.15(rps), and calculating the viscosity of the lubricating layer of the pumped cement-based composite material.
The test results are shown in Table 3.
TABLE 3
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (7)
1. A method for improving the rheological property of a PVA fiber and nano-silica cement-based composite material is characterized in that the PVA fiber with the length-diameter ratio of 100-300 is added.
2. The method for improving the rheological property of the PVA fiber and nano-silica cement-based composite material according to claim 1, wherein the PVA fiber with the length-diameter ratio of 200-300 is added.
3. The method of improving the rheological properties of a PVA fiber and nanosilica cement-based composite material according to claim 2, wherein the PVA fiber is incorporated in an amount of 0.3% to 1% by volume.
4. The method of improving the rheological properties of PVA fibers and nanosilica cement-based composite materials according to claim 3, wherein the PVA fibers are incorporated at a volume level of from 0.3% to 0.8%.
5. The method of improving the rheological properties of PVA fibers and nanosilica cement-based composite materials according to claim 4, wherein the PVA fibers are incorporated at a volume level of from 0.3% to 0.5%.
6. The method for improving the rheological property of a PVA fiber and nano-silica cement-based composite material according to claim 1, wherein a mixed material comprising copper slag, gypsum, volcanic ash, metakaolin and fly ash is added.
7. The method for improving the rheological property of the PVA fiber and nano-silica cement-based composite material according to any one of claims 1 to 6, comprising the following steps:
s1, mixing cement and a mixed material, adding 1/2 mass of water, and pre-mixing for 20-30 s to obtain mortar;
s2, mixing the nano SiO2Mixing the particles with a water reducing agent, adding the mixture into the residual water, stirring and dispersing, adding the mixture into the mortar after the mixture is uniformly dispersed, and stirring for 1-2 min to obtain a mixed material;
and S3, adding PVA fibers into the mixture obtained in the S2, and uniformly stirring.
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| CN115519670A (en) * | 2022-10-20 | 2022-12-27 | 大庆长垣能源科技有限公司 | Preparation process of tough-elastic cement slurry for gas storage well cementation |
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| CN114890758A (en) * | 2022-05-13 | 2022-08-12 | 四川华能泸定水电有限公司 | Cement-based material for 3D printing |
| CN115519670A (en) * | 2022-10-20 | 2022-12-27 | 大庆长垣能源科技有限公司 | Preparation process of tough-elastic cement slurry for gas storage well cementation |
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