CN112279547A - Composition solution and method for removing surface crystals of low-alkali sulphoaluminate cement product - Google Patents
Composition solution and method for removing surface crystals of low-alkali sulphoaluminate cement product Download PDFInfo
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Abstract
The invention discloses a composition solution and a method for expelling crystals on the surface of a low-alkali sulphoaluminate cement product. The composition solution includes a structural modification material and a hole blocking material. The structural modification material is prepared by mixing the following components in percentage by volume: 0.01-1.0% of gallic acid aqueous solution 5.0-12.0%, 0.01-1.0% of lignin sulfonic acid aqueous solution 5.0-12.0% and water 76.0-90.0%. The cavity sealing material is prepared by mixing the following components in percentage by volume: 0.06% -1.5% of glycine aqueous solution 4.0-10.0%, 0.06% -1.5% of alanine aqueous solution 4.0-10.0% and water 80.0-92.0%. And respectively filling the structure modification material and the cavity sealing material into a structure modification pool and a cavity sealing pool, and soaking the cement product in the structure modification pool and the cavity sealing pool for 12 and 24 hours in sequence to realize the removal of the surface crystals of the low-alkali sulphoaluminate cement product. The invention is mainly characterized in that the composition solution is an aqueous solution which is green, tasteless, nontoxic and safe; only the components are directly mixed, and the preparation and use methods are simple and reliable.
Description
Technical Field
The invention belongs to the technical field of cement product manufacture, and particularly relates to a technology for removing surface crystals of a low-alkali sulphoaluminate cement product by using a composition solution.
Background
With the development of cement technology, special cement and special cement are researched and developed in all countries in the world. In 1975 sulphoaluminate cement was developed, which has low alkaline characteristics and finds application in the manufacture of flowerpots, flower pots, fountains, plastic-stone rockery, garden rockery and the like. However, technical bottlenecks such as crystal precipitation caused by alkali return on the surface of the sulphoaluminate cement product often occur, so that the product appearance is seriously influenced, and the market competitiveness and the export foreign exchange capacity are lost. Although the technical bottleneck can be solved by optimizing the formula of the product material and the process parameters, the phenomenon that crystals or hair are precipitated on the surface of the product due to surface alkali return always troubles manufacturers, and becomes an urgent research hotspot for low-alkali sulphoaluminate cement products. Some factories and households use 10% of dilute strong acid and mixed liquor thereof, cation silicone-acrylic emulsion alkali-resistant seal primer, cement-based permeable crystalline waterproof paint, facing pasting technology and other alkali-resistant seal surfaces, and the alkali-resistant seal surfaces are treated by sulphoaluminate dry-mixed mortar, garden stone binder, saltpetering inhibitor, low-salt and alkali-resistant material adjustment formula, saltpetering scavenger and other materials, but the technical problem that crystals are separated out due to surface alkali return cannot be solved, and the phenomenon that crystals or hair are separated out on the surface of a product seriously influences the production and export foreign exchange of the product. The technology for removing the alkali-returning crystallization of the low-alkali sulphoaluminate cement product becomes a research hotspot of scholars and manufacturers at home and abroad, and has important scientific and technological significance and economic value for promoting the production and application of the low-alkali sulphoaluminate cement product, improving the viewing value, market competitiveness and export foreign exchange capacity of garden rockery and the like.
Disclosure of Invention
The invention aims to provide a composition solution and a method for removing surface crystals of low-alkali sulphoaluminate cement products, aiming at the technical defect of alkali reversion and crystallization of the existing low-alkali sulphoaluminate cement products.
The specific technical scheme of the invention is as follows:
a composition solution for driving off surface crystals of low-alkali sulphoaluminate cement products comprises a structure modification material solution and a cavity blocking material solution, wherein the structure modification material is gallic acid, lignosulfonic acid or sodium salt solution thereof, or gallic acid, lignosulfonic acid or potassium salt solution thereof; the cavity blocking material is amino acid.
In the present invention, the structural modification material solution includes, by volume: 5.0-12.0% of gallic acid aqueous solution with the mass volume ratio of 0.01-1.0%, 5.0-12.0% of lignosulfonic acid aqueous solution with the mass volume ratio of 0.01-1.0%, and 76.0-90.0% of water.
In a preferred embodiment of the present invention, the solution of the hole blocking material comprises, by volume: 4.0-10.0% of glycine aqueous solution with the mass volume ratio of 0.06-1.5%, 4.0-10.0% of alanine aqueous solution with the mass volume ratio of 0.06-1.5% and 80.0-92.0% of water.
Preferably, the structural modification material solution comprises the following components in percentage by volume:
5.0-12.0% of 1.0% gallic acid aqueous solution;
5.0-12.0% of 1.0% lignosulfonic acid aqueous solution;
90.0-76.0% of water.
Preferably, the cavity blocking material comprises the following components in percentage by volume:
4.0-10.0% of 1.5% glycine aqueous solution;
4.0-10.0% of 1.5% alanine aqueous solution;
92.0-80.0% of water.
The mechanism of the invention is as follows:
the main component of the low-alkalinity sulphoaluminate cement product is anhydrous calcium sulphoaluminate (CaAlO)3S), dicalcium silicate (2 CaSiO)3) And tricalcium silicate (3 CaSiO)3) And the like, the following reaction occurs during cement hydration:
CaAlO3S+H2O→H4AlO3S+Ca(OH)2 (1)
2CaSiO3+H2O→2H2SiO3+Ca(OH)2 (2)
3CaSiO3+H2O→2H2SiO3+Ca(OH)2 (3)
Ca(OH)2→Ca2++OH－ (4)
as can be seen, a great deal of Ca (OH) exists in the cement product2、Ca2+NaOH, KOH, etc. [15 ]]Ca (OH) when the product loses water on drying2、Ca2+The components such as NaOH and KOH can gradually migrate outwards along capillary pores along with free water, and the components are subjected to first saltpetering crystallization precipitation outside the cement product; ca (OH) in the Water curing stage2、Ca2+Soluble components such as NaOH and KOH are dissolved and brought to the surface, and then the mixture is dried to generate secondary efflorescence crystallization. Further, Ca (OH)2Absorbing CO in air2Will form CaCO3. Apparently, Ca (OH)2、Ca2+、CaCO3、NaOH、KOH、H2O is a main cause of the saltpetering crystallization of the cement product, and the surface roughness, the porosity or the like of the internal structure of the cement product are external causes of the saltpetering crystallization of the cement product.
The invention adopts gallic acid (HOOC-phi)-R), Lignosulfonic acid ((HO)3S)2-phi-R) is a new material for structural modification.
Gallic acid
Lignosulfonic acid sodium salt
When the sample of the cement block containing the crystals is soaked in a 1 percent solution of the new material (C) for structural modification for 12 hours, the gallic acid, the lignosulfonic acid and Ca (OH) on the outer surface of the cement product2Free Ca2+The reaction generates insoluble calcium gallate, calcium lignosulfonate and the like, so that crystals are dissolved and enter a liquid phase from a solid phase, cavities are left on the surface of the cement product, and the crystals on the surface of the cement product are effectively removed, wherein possible reactions are shown as follows;
HOOC-Φ-R+Ca(OH)2→Ca(OOC)2-Φ-R+H2O (5)
(HO3S)2-Φ-R+Ca(OH)2→Ca(O3S)2-Φ-R+H2O (6)
HOOC-Φ-R+Ca2+→Ca(OOC)2-Φ-R+H+ (7)
(HO3S)2-Φ-R+Ca2+→Ca(O3S)2-Φ-R+H+ (8)
HOOC-Φ-R+CaCO3→Ca(OOC)2-Φ-R+H2CO3 (9)
(HO3S)2-Φ-R+CaCO3→Ca(O3S)2-Φ-R+H2CO3 (10)
H2CO3→CO2↑+H2O (11)
the gallic acid and the lignosulfonic acid can also respectively react with NaOH and KOH, so that NaOH and KOH crystals on the surface of the cement product are dissolved and enter a liquid phase from a solid phase, and cavities are left on the surface of the cement product, and the crystals on the surface of the cement product are effectively removed;
HOOC-Φ-R+NaOH→NaOOC-Φ-R+H2O (12)
(HO3S)2-Φ-R+NaOH→Na2(O3S)2-Φ-R+H2O (13)
HOOC-Φ-R+KOH→KOOC-Φ-R+H2O (14)
(HO3S)2-Φ-R+KOH→K2(O3S)2-Φ-R+H2O (15)
to inhibit Ca free outside the cavity2+By penetration with an amphoteric active substance (e.g. an amphoteric amino acid, such as glycine, HOOC-R-NH)2) As a blocking agent. When the cavity cement product is left to be soaked in 1 percent of sealing new material (B) solution for 24 hours, the active substance HOOC-R-NH2Holes left by exfoliation of the intercalated crystals, HOOC-groups and Ca2+The following reactions occur:
HOOC-R-NH2+Ca2+→Ca(OOC)2-R-NH2 (16)
Ca(OOC)2-R-NH2ca (OOC) in molecule2End facing inwards, NH2The end-to-end occupation of the cavity sites or the plugging of the pores automatically forms an inert seal and finally the seal is painted over, thus preventing the growth or generation of crystals inside and on the outer surface of the cement sample.
In a preferred embodiment of the composition solution of the invention,
the structural modification material solution comprises the following components in percentage by volume:
1.0% (w/v) aqueous solution of gallic acid 5.0;
1.0% (w/v) aqueous lignosulfonic acid solution 5.0%;
and (5) 90.0 percent of water.
The cavity blocking material solution comprises the following components in percentage by volume:
1.5% (w/v) glycine aqueous solution 4.0%;
1.5% (w/v) aqueous alanine solution 4.0%;
92.0 percent of water.
In a preferred embodiment of the composition solution of the invention,
the structural modification material solution comprises the following components in percentage by volume:
1.0% (w/v) aqueous solution of gallic acid 8.0%;
1.0% (w/v) aqueous lignosulfonic acid solution 8.0%;
and (5) 84.0 percent of water.
The cavity blocking material solution comprises the following components in percentage by volume:
1.5% (w/v) aqueous glycine solution 7.0%;
1.5% (w/v) aqueous alanine solution 7.0%;
and (5) 86.0 percent of water.
In a preferred embodiment of the composition solution of the invention,
the structural modification material comprises the following components in percentage by volume:
1.0% (w/v) gallic acid aqueous solution 12.0%;
1.0% (w/v) aqueous lignosulfonic acid solution 12.0%;
76.0 percent of water.
The cavity blocking material solution comprises the following components in percentage by volume:
1.5% (w/v) glycine aqueous solution 10.0%;
1.5% (w/v) alanine aqueous solution 10.0%;
80.0 percent of water.
The invention has the beneficial effects that:
1. the composition solution is an aqueous solution, is green, tasteless, nontoxic and safe;
2. the composition solution only needs to directly mix all the components, and the preparation and use methods are simple and reliable;
3. the composition solution of the invention can be used continuously;
4. the crystal expelling technology of the composition solution is efficient, the treatment cost is low, and the economic benefit is high;
5. the composition solution of the invention does not produce secondary pollution and has wide application range.
Drawings
FIG. 1 is a schematic diagram of the technical scheme of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
In the following embodiments, the structural modification material (C) and the cavity sealing material (B) are respectively placed in a structural modification tank and a cavity sealing tank, the cement product is sequentially soaked in the structural modification tank and the cavity sealing tank for 12 and 24 hours, the surface crystals of the low-alkali sulphoaluminate cement product can be removed, and then the cement product is dried and painted.
The composition solution can be used continuously.
Example 1
The composition solution for expelling the surface crystals of the low-alkali sulphoaluminate cement product consists of a structure modification material and a cavity sealing material.
The structural modification material is prepared by mixing the following components in percentage by volume:
5.0% gallic acid water solution;
1.0% aqueous lignosulfonic acid solution 5.0%;
and (5) 90.0 percent of water.
The cavity sealing material is prepared by mixing the following components in percentage by volume:
4.0% of 1.5% glycine aqueous solution;
4.0% of 1.5% alanine aqueous solution;
92.0 percent of water.
The composition solution can be automatically packaged and stored after being uniformly mixed.
The experimental method comprises the following steps:
experimental groups: 60 cement products (round fountain, 3.14 (0.2)2)×0.6＝0.075m3) Soaking the hollow cavity sealing material in a soaking liquid pool for 12h, taking out, and soaking the hollow cavity sealing material for 24 h.
Control group: 60 cement products (round fountain, 3.14 (0.2)2)×0.6＝0.075m3) Soaking in water in a soaking pool for 12h +24 h.
The application effect is shown in table 1.
TABLE 1 Effect and cost of practical application of the technique for driving off surface crystals of low alkali sulphoaluminate cement products of example 1
As can be seen from table 1, after the low-alkali sulphoaluminate cement product is respectively soaked in the structural modification material, the cavity sealing material and other composition solutions for 12 hours and 24 hours, the cement product has smooth appearance, no alkali return crystallization after 30 days, better folding strength and the like than water soaking treatment, the material can be repeatedly used, and the cost is low, which shows that the effect of practical application of the technology for removing the surface crystal of the low-alkali sulphoaluminate cement product is obvious, and the technology is economical and practical.
Example 2
The composition solution for expelling the surface crystals of the low-alkali sulphoaluminate cement product consists of a structure modification material and a cavity sealing material.
The structural modification material is prepared by mixing the following components in percentage by volume:
1.0% aqueous solution of gallic acid 8.0%;
1.0% aqueous lignosulfonic acid solution 8.0%;
and (5) 84.0 percent of water.
The cavity sealing material is prepared by mixing the following components in percentage by volume:
7.0% of 1.5% glycine aqueous solution;
1.5% alanine water solution 7.0%;
the composition solution can be automatically packaged and stored after being uniformly mixed.
The experimental method comprises the following steps:
experimental groups: 30 cement products (Square fountain, 0.6X 0,4 ═ 0.144 m)3) Soaking the hollow cavity sealing material in a soaking liquid pool for 12h, taking out, and soaking the hollow cavity sealing material in the soaking liquid pool for 24 h.
Control group: 30 cement products are soaked in water in a soaking pool for 12h +24 h.
The application effect is shown in table 2.
TABLE 2 Effect and cost of practical application of the technique for driving off surface crystals of low alkali sulphoaluminate cement products of example 2
As can be seen from Table 2, after the low-alkali sulphoaluminate cement product is soaked in the structural modification material, the cavity sealing material and other composition solutions in sequence for 12 to 24 hours, the cement product has smooth appearance, no alkali return crystallization after 30 days, better breaking strength and the like than water soaking treatment, the material can be repeatedly used, and the cost is low, thereby showing that the effect of practical application of the technology for removing the crystal on the surface of the low-alkali sulphoaluminate cement product is obvious, and the method is economic and practical.
Example 3
The composition solution for expelling the surface crystals of the low-alkali sulphoaluminate cement product consists of a structure modification material and a cavity sealing material.
The structural modification material is prepared by mixing the following components in percentage by volume:
1.0% aqueous solution of gallic acid 12.0%;
1.0% aqueous lignosulfonic acid solution 12.0%;
76.0 percent of water.
The cavity sealing material is prepared by mixing the following components in percentage by volume:
10.0% of 1.5% glycine aqueous solution;
1.5% alanine aqueous solution 10.0%;
80.0 percent of water.
The composition solution can be automatically packaged and stored after being uniformly mixed.
The experimental method comprises the following steps:
experimental groups: 30 cement products (rockery fountain, 0.3X 0.6X 0,8 ═ 0.144m3) Soaking the hollow cavity sealing material in a soaking liquid pool for 12h, taking out, and soaking the hollow cavity sealing material in the soaking liquid pool for 24 h.
Control group: 30 cement products (rockery fountain, 0.3X 0.6X 0,8 ═ 0.144m3) Soaking in water in the soaking pool for 12h +24 h.
The application effect is shown in table 3.
TABLE 3 Effect and cost of practical application of the technique for driving off surface crystals of low alkali sulphoaluminate cement products of example 3
As can be seen from table 3, after the low-alkali sulphoaluminate cement product is soaked in the structural modification material, the cavity sealing material and other composition solutions in sequence for 12 to 24 hours, the cement product has smooth appearance, no alkali return crystallization after 30 days, better breaking strength and other specific water soaking treatment, the material can be used repeatedly, and the cost is low, which shows that the effect of practical application of the technology for removing the crystal on the surface of the low-alkali sulphoaluminate cement product is obvious, and the technology is economic and practical.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (9)
1. The composition solution for expelling the surface crystals of the low-alkali sulphoaluminate cement product comprises a structure modification material solution and a cavity sealing material solution, wherein the structure modification material is gallic acid, lignosulfonic acid or sodium salt thereof, or gallic acid, lignosulfonic acid or potassium salt thereof; the cavity blocking material is amino acid.
2. The composition solution of claim 1, wherein: the structural modification material solution comprises the following components in percentage by volume: 5.0-12.0% of gallic acid aqueous solution with the mass volume ratio of 0.01-1.0%, 5.0-12.0% of lignosulfonic acid aqueous solution with the mass volume ratio of 0.01-1.0%, and 76.0-90.0% of water.
3. The composition solution of claim 1, wherein: the cavity sealing material solution comprises the following components in percentage by volume: 4.0-10.0% of glycine aqueous solution with the mass volume ratio of 0.06-1.5%, 4.0-10.0% of alanine aqueous solution with the mass volume ratio of 0.06-1.5% and 80.0-92.0% of water.
4. The composition solution of claim 1, wherein:
the structural modification material solution in the composition solution comprises the following components in percentage by volume:
5.0-12.0% of 1.0% gallic acid aqueous solution;
5.0-12.0% of 1.0% lignosulfonic acid aqueous solution;
76.0-90.0% of water;
the cavity blocking material solution in the composition solution comprises the following components in percentage by volume:
4.0-10.0% of 1.5% glycine aqueous solution;
4.0-10.0% of 1.5% alanine aqueous solution;
80.0-92.0% of water.
5. The composition solution of claim 1, wherein:
the structural modification material solution in the composition solution comprises the following components in percentage by volume:
5.0% of 1.0% gallic acid aqueous solution;
1.0% aqueous lignosulfonic acid solution 5.0%;
90.0% of water;
the cavity blocking material solution in the composition solution comprises the following components in percentage by volume:
4.0% of 1.5% glycine aqueous solution;
4.0% of 1.5% alanine aqueous solution;
92.0 percent of water.
6. The composition solution of claim 1, wherein:
the structural modification material solution in the composition solution comprises the following components in percentage by volume:
1.0% aqueous solution of gallic acid 8.0%;
1.0% aqueous lignosulfonic acid solution 8.0%;
84.0 percent of water;
the cavity blocking material solution in the composition solution comprises the following components in percentage by volume:
7.0% of 1.5% glycine aqueous solution;
1.5% alanine water solution 7.0%;
and (5) 86.0 percent of water.
7. The composition solution of claim 1, wherein:
the structural modification material solution in the composition solution comprises the following components in percentage by volume:
1.0% aqueous solution of gallic acid 12.0%;
1.0% aqueous lignosulfonic acid solution 12.0%;
76.0 percent of water;
the cavity blocking material solution in the composition solution comprises the following components in percentage by volume:
10.0% of 1.5% glycine aqueous solution;
1.5% alanine aqueous solution 10.0%;
80.0 percent of water.
8. The method for expelling the surface crystals of the low-alkali sulphoaluminate cement product is characterized by comprising the following steps: and sequentially putting the low-alkali sulphoaluminate cement product into the structural modification material solution and the cavity sealing material solution and fully soaking the products respectively.
9. The method of claim 8, wherein: the soaking time of the cement product in the structural modification material solution is 10-12 h; soaking in the hole sealing material solution for 20-24 h.
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| JPS52124021A (en) * | 1976-04-13 | 1977-10-18 | Ajinomoto Kk | Intimate mixing agent of cement mortar or concrete |
| JPS59164664A (en) * | 1983-03-10 | 1984-09-17 | 三洋化成工業株式会社 | Efflorescence preventer for cement products |
| CN101913794A (en) * | 2010-08-13 | 2010-12-15 | 江苏尼高科技有限公司 | Cement mortar saltpetering inhibition additive |
| CN105481326A (en) * | 2015-12-30 | 2016-04-13 | 卓达新材料科技集团威海股份有限公司 | Alkali efflorescence prevention sulphate aluminium cement product and preparation method thereof |
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2020
- 2020-11-09 CN CN202011239235.8A patent/CN112279547A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52124021A (en) * | 1976-04-13 | 1977-10-18 | Ajinomoto Kk | Intimate mixing agent of cement mortar or concrete |
| JPS59164664A (en) * | 1983-03-10 | 1984-09-17 | 三洋化成工業株式会社 | Efflorescence preventer for cement products |
| CN101913794A (en) * | 2010-08-13 | 2010-12-15 | 江苏尼高科技有限公司 | Cement mortar saltpetering inhibition additive |
| CN105481326A (en) * | 2015-12-30 | 2016-04-13 | 卓达新材料科技集团威海股份有限公司 | Alkali efflorescence prevention sulphate aluminium cement product and preparation method thereof |
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| Title |
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| 李乃珍等: "《特种水泥与特种混凝土》", 30 September 2010, 中国建材工业出版社 * |
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