CN101265069A - High-strength water-resistant plastering gypsum and producing method thereof - Google Patents

Abstract

The invention relates to a high-strength water-proof gypsum plaster and a production method thereof. The inventive high-strength water-proof gypsum plaster is made from the following materials in weight proportions: 10-99% of gypsum-based composite binding agent, 0-90% of aggregates, 0.08-4% of additives and 0-16.1% of adsorbent. The production method comprises the following steps: weighing raw materials at the given ratio, drying the aggregates, mixing all raw materials, and packaging. The inventive high-strength water-proof gypsum plaster has high strength and good water resistance; can be made from chemical gypsum materials without needing calcination, such as desulfurized gypsum, phosphogypsum, fluorgypsum and citric acid gypsum; and has the advantages of low production cost, energy conservation, discharge reduction and environmental friendliness.

Description

A high-strength plaster and water Technical Field The present invention relates to a high-strength water-resistant gypsum plaster based composite material and method for producing, in particular, it relates to a building interior, for external walls and roof panels plaster surface of the high-strength water-resistant gypsum stucco and plaster production bACKGROUND firmly bonded to the substrate having, fast setting and hardening, setting and hardening without shrinkage, easy construction, high work efficiency, avoid the traditional cement mortar layer surface cracking, hollowing, shedding drawback, especially for plastering aerated concrete shear walls and wall. In other countries, the use of plaster has been quite common, such as Germany, more than 70% of the material is plaster wall plaster, wall plaster Britain 50% of the total cast. Began research and development on our wall plaster the early 1980s, has now formed four major categories, dozens of varieties, these four categories of dozens of varieties from plaster wall plaster powder phase classification, that is half the water phase plaster , n-type anhydrite plaster mixed phase type plaster (hemihydrate plaster and anhydrite mixed ns, the intensity obtained from a pre-hydrated gypsum hemihydrate, anhydrite and late strength obtained by the hydration ns, so that the wall plaster after the wall having a continuous process and the strength increasing hydration process), and gypsum, lime plaster mixed. Three in the front wall plaster, can be divided into the surface layer, insulation layer and plaster, and plaster, lime plaster mixed applies only to the surface layer, it constitutes dozens of varieties of plaster. In the above ten kinds of plaster, the plaster after hydration and hardening, which is the basic structure of gypsum, gypsum dihydrate low strength, poor water resistance (low softening coefficient), and the need to calcination, high production costs. Our country is a vast, great stuff, the North-South differences in climate, Northwest drier, air-dried, southern rainy, humid air, especially in the rainy season, the air relative humidity is above 80%, and regardless of the North and the South, its kitchen and bathroom total moist air is in a state, the traditional plaster should not be used in these environments. Therefore, the need to improve the water resistance of wall plaster. Moreover, China's current annual industrial by-product phosphogypsum 2,000 tons, and a rate of 15% a year; gypsum produced annually by 400 million tons per year will be added in 2010 after more than 20 million tons of gypsum; Further, there are a lot of fluorine gypsum, gypsum lemon, boron gypsum, titanium gypsum, gypsum and other salts (wherein fluorgypsum anhydrous gypsum, anhydrite also known as anhydrite, gypsum, phosphogypsum, lemon gypsum, gypsum boron , titanium gypsum and gypsum and other salts are gypsum), these industrial by-product gypsum plaster, also known as chemical, only a small amount of additives used in cement, piling up the majority in the state, not only occupy a lot of land, but also pollute the environment and groundwater resources. Object of the present invention to overcome some of the drawbacks of the prior plaster, there is provided a high-strength plaster water, and without the use of chemical gypsum calcined gypsum, phosphogypsum, fluorgypsum, lemon and the like as raw materials for the preparation of gypsum, both reduce the production cost of plaster, but also conducive to energy conservation, environmental protection. Object of the present invention is achieved by the following technical solution: The present invention water-resistant high-strength plaster from the following materials and the composition ratio by weight: 10% ~99% gypsum-based composite cementitious material (preferably 40% ~ 70%), aggregate 0~90% (preferably 30% ~69%), 4% additive 08~ 0.5, 1% adsorbent 0~16; the gypsum binder based composite material consists of the following components: mixing gypsum powder 40% ~ 80% (preferably 50% ~ 70%), active admixture 10% ~ 45% (preferably 15% ~ 35%), a basic activator 4% ~ 15% (preferably SUMMARY invention is selected from 6% ~ 12%) , redispersible powder 0.1% ~ 2% coagulant, 0% ~ 6% (preferably 1% ~ 3%), lime 0~ 5%, 0~1% early strength agent, superplasticizer 0~ 1%, fiber 0~1.0%; mixing gypsum powder is selected from the gypsum powder a powder anhydrite or mixtures thereof; the gypsum powder may be natural gypsum powder, gypsum powder, gypsum powder pretreated or pretreated phosphorus gypsum powder lemon; preferred formulation, gypsum dihydrate: anhydrite = 30% ~ 90%: 10% ~ 70%; 0~15% may be added if necessary hemihydrate gypsum (P-CaS (v | H20 or a -CaS04 * | H20); 60 mesh ~ 500 mesh powder (preferably 8 0 mesh ~ 200 mesh); the anhydrite anhydrite n is a finely divided powder or direct Fluorgypsum grinding anhydrite, gypsum, or by 360~ lOO (TC calcined form, including 360~50 ( slowly soluble anhydrite n -S TC calcined form, 500~70 (insoluble anhydrite calcined TC II form a U, 700~100 (TC casting anhydrite II form a calcined E; fluoro-gypsum, anhydrite II-S , E anhydrite II a particle size of 80~300 mesh (preferably 100~250 mesh); natural anhydrite, anhydrite n-U particle size of a particle size of 100~500 mesh (250~ 400 mesh); the active powder (plaster cast) selected from quenched slag ground water (i.e., water-quenched blast furnace slag ground), ground fly ash, ground slag refining iron, iron alloy ground slag, silicon lithium ground slag powder, silica fume, ground mixture of fine powder of one fluoro or two or more kinds, preferred embodiment of the fly ash and the mixture of both water quenched slag, as a more preferred embodiment, the mixture ratio of fly ash: water quenched slag = 1: I; the alkaline stimulating agent is Portland cement, cement, cement, stone, carbide slag or alkali slag; the coagulant Selected Na2S04, K2S04, NaHS04, KHS04, CuS04, FeS04, AL2 (S04) 3, ZnS04, KAL (SO4) 2 * 12H20), K2Cr207 mixture of one or two or more, preferably NaHS04, Na2S04, KAL ( SO4) 2,12H20), K2Cr207 one kind or a mixture of two or more; coagulant grinding to a particle size "100 mesh; the adsorbent is an active clay, attapulgite, activated attapulgite clay available chabazite, mordenite zeolites, activated carbon, montmorillonite, sepiolite powder, a diatomaceous earth or a mixture of two or more powders; to join plaster adsorbent chamber can absorb harmful gases, such as formaldehyde, benzene, toluene, ammonia, carbon monoxide, so called ecological plaster. The early strength agent, water reducing agents are well-known cement early strength agent, water-reducing agent; the aggregate is quartz sand and / or limestone powder, particle size less than 4mm; the additive is the MC methylcellulose, entraining agents, starch ethers, thixotropic lubricants, one defoamer or a mixture of several species; methyl cellulose, hydroxyethyl methyl cellulose ethers available MC of MHEC, hydroxypropyl methyl cellulose ethers (MHPC) , hydroxyethyl cellulose (HEC); to the air-entraining agent is known air-entraining agents, it was stirred in a mortar can be introduced during the distribution of a large number of uniform, stable, micro bubbles blocking additives, such as micro mortar foam agents. Production method: Each material for weighing a predetermined ratio, and the drying aggregate, and all the ingredients mixed, packaging, Serve. The present invention is anhydrous gypsum, dihydrate gypsum and active admixture as the main raw material, addition of an alkaline activator excitation, anhydrous gypsum dissolves, gypsum crystals and generates a small amount of ettringite crystals skeleton structure, unhydrated particles of gypsum dihydrate, anhydrous gypsum and particles of active aggregate particles for the micro-aggregate fill in the gap, the dissolved gypsum, hydrated silicate or aluminate bonding effect of the components of the binding material together to form a composite material microstructure of the hardened gypsum based. This microstructure makes plaster has good water resistance and high strength. Because the hydration products of gypsum hardened body was poor water resistance of gypsum crystals, and the cured composite gypsum binder and the active elicitor admixture formed increases the amount of low solubility in water hardening Portland hydrogel or aluminate gel and a small amount of ettringite, gels or silicates and aluminates gel part is coated gypsum crystals and unhydrated gypsum and anhydrous gypsum particle surface, dimethyl gypsum and anhydrous gypsum protective package, to prevent water erosion and weakening of the plaster, thereby increasing the strength and water resistance of the plaster. By controlling the proportions of the components of the material, gypsum-based composite material ettringite generated little, no damaging effect on the hardened gypsum-based composites. The present invention may also be utilized without industrial byproduct gypsum calcined gypsum, phosphogypsum, fluorgypsum, lemon and the like as raw materials for the preparation of gypsum, plaster can reduce the production cost, and is also beneficial to energy saving and reduction of industrial byproduct gypsum occupies pollution of land and water resources, to protect the environment <= DETAILED DESCRIPTION the following embodiments in conjunction with embodiments of the present invention will be further described. (A) a base material plaster ratio optimization Experimental Example (1) Materials: gypsum powder is a natural gypsum, natural anhydrite powder (particle size of 100 mesh), active admixture is ground water quenched slag, alkaline activator is portland cement (# 325), the coagulant is alum [KA1 (S04) 2 * 12H20] (100 mesh size), the MC-methyl cellulose, redispersible powders, the respective components of the feed the weight ratio of: gypsum: anhydrite: water quenched slag: cement: alum: the MC: redispersible powder = 63.6: 0: 27.3: 9.1: 3.0: 0.1: 1.02 # = 58.6: 5: 27.3 : 9.1: 3.0: 0.1: 1.03 * = 53.6: 10: 27.3: 9.1: 3.0: 0.1: 1.04 # = 43.6: 20: 27.3: 9.1: 3.0: 0.1: 1.05 # two 38.6: 25: 27.3: 9. 1: 3.0: 0.1: 1.06 * = 31.8: 3.18: 27.3: 9.1: 3.0: 0.1: 1.07 28.6 # =:: 35: 27.3:: 91: 3.0: 0.1: 1.08 = 23.6 *:: 40: 27.3:: 91: 3.0: 0.1: 1.09 = 18.6 *:: 45: 27.3:: 91: 3.0: 0.1: 13.6 = 1.010 *:: 50: 27.3:: 91: 3.0 : 0.1: 1.011 # = 0:: 636: 27.3:: 9.1: 3.0: 0.1: 1.0 ratio as described above, weighed raw materials were mixed Absorbed, add water, stir, cement ratio 0.35, casting molding, die size 40 X 40 X 160mm, according to GB / T1346-2001 measuring clotting time, according to GB / T17671-1991 measured 28 days bending, compressive strength, and the foam was measured water wet compressive strength 72 hours (calculated softening coefficient), by GB / T2419-2005 measured stucco gypsum fluidity, by JC / T517-93 DIN1168-2 or bond strength test standard. The results in Table l. Table l optimization plaster matrix material (a) Sample Initial setting time results final setting time Compressive strength Bending strength bond strength softening coefficient min min Mpa Mpa Mpa% 1 * 520 - 3.5 23. 3 0. 5 0. # 832 24.5 0.5 310 480 3.8 145 283 3.7 0.843 28.4 # 0.55 # 0.844 32.1 0.55 120 183 3.8 105 178 3.7 0.845 * 0.53 0.836 34.2 3.8 90 178 39 * . 2 0. 52 0. 847 # 98 188 3.9 42. 6 0. 52 0.848 # 108 198 4.2 43. 8 0.53 0. 849ff 120 240 3.8 39. 2 0. 54 0. 8410 # 130 252 3.9 35. 0 0 . 52 0. 84IIs 152 300 3.9 33, 0 0. 54 0.84 table 1 is optimized plaster base material results, it can be seen, except for # 1 and # 2 specimens, 3S~ 11 # samples were satisfied JC / standard T517-93, bending, compression strength, bond strength far exceeds JC / T517-93 standards, and good water resistance. This experiment determined that the high-strength water-resistant material component plaster, anhydrite ranges greater than 5%, and therefore, the original weight of the composition of the material sample # 3 # ~ 11 ratio can be used as wall plaster surface composition weight ratio, i.e., anhydrite dosage greater than or equal to 10%. (Ii) Optimization of plaster base material Example (2) Experimental material ratio: gypsum dihydrate gypsum in place (water content 0.5%, particle size 200 mesh), calcined phosphogypsum with 900'C (anhydrite II-E , 200 mesh size) instead of anhydrite, active admixture is ground water quenched slag and ground fly l: 1 mixture of alkaline activator is portland cement (325 ", the coagulant is alum sodium l: l mixture of ((120 mesh size), Mc, redispersible powder, the weight ratio of the components of the raw materials: stone desulfurization, anhydrite II-E: active admixture: cement: listen pro : the MC: 12 * can be subdivided two Xie 40.45: 40.45: 10: 9.1: 4.0: 0.1: 1.013 = 37 # 95: 37.95: 15: 9.1: 4.0: 0 1: # = 1.014 35 45 35.45: 20: 9.1: 4.0: 0.1: 1.015 # = 30 45: 30.45: 27.3: 9.1: 4.0: 0.1: 1.016 * = 25 45: 25.45: 40: 9.1: 4.0: 0.1: 1.017 # = 20 45: 20.45: 50: 9.1: 4.0: 0.1: 1.018 * = 33 45. : 33. 45: 27.3: 3. 1: 4.0: 0. 1: 1.019 * = 31 95:. 31.9: 27.3: 6. 1: 4.0: 0. 1: 1.020fl = 30 45:. 30. 45: 27.3 : 9.1: 4.0: 0.1: 28 = 1.0218. 95: 28. 95: 27.3: 12.1: 4.0: 0. 1: 1.022s = 27 45 27.45:. 27.3: 15. 1: 4.0 0. 1: 1.023fl = 25 95 25. 95:. 27.3: 18. 1 : 4.0 Lu 0.1: 1.0 Weigh the raw materials according to the above ratio, homogeneous mixing with water, cement ratio 0.35, casting molding, press GB / T17671 - measurement sample 28 days compressive strength and flexural strength of 1999, softening coefficient, press 2 DIN1168 a measured bond strength, results in table 2. table 2 plaster matrix material optimization experiments (b) test results sample bending strength compressive strength Mpa Mpa% bond strength softening coefficient Mpa12 * 2.8 13.6 0. 45 0.5513 15.2 * 2.9 * 3.0 0.60 0.5414 24.3 0.80 0.5415 35.0 * 3.6 * 4.0 0.82 0.5416 42.0 0.85 0.5217 38.3 0.85 3.6 # 0 . 5218s 2.6 17.6 0. 57 0. 5519ff 2.9 19.8 0. 62 0. 5520s 3.4 35.2 0. 83 0. 5521 # 3.5 42. 1 0. 84 0. 5322s 3.2 44.3 0. 85 0. 5323B 3.0 38. 1 0 83 0.53 table 2 is a high-strength water-resistant wall plaster material of the active component results in admixture and the cement content, table 2 Note: with the dosage of active admixture material increases, intensity increases, softening coefficient increase, when the active admixture is increased to 40% (1 6FL), the maximum strength, but also increases the expansion, sample was soaked in water for 30 days, the sample surface microcracks, so active admixture dosage should be less than 40%. Table 2 also suggests the other hand: with increasing cement content, the strength is improved softening coefficient increases, but when the cement content is increased to 15%, a sample soaked in water for 30 days, a partial surface microcracks when the cement content is increased to 18%, sample was soaked in water for 30 days, the sample surface cracks, softening coefficient combined, comprehensive analysis of strength, plaster matrix material, reactive admixture should be greater than 15%, less than 40%, 6% cement content should be greater than, less than or equal to 15%. (C) high-strength water-resistant bottom wall plaster aggregate optimized ratio of raw materials Experimental Example: instead of gypsum plaster pretreated with phosphorus (particle size 150 mesh), 70 (TC calcined gypsum (II a hard gypsum E, particle size of 250 mesh) instead of anhydrite, an alkaline agent is excited aluminate cement (# 425), active admixture is ground water quenched slag, the coagulant is alum (IOO mesh particle size), the choice of sand aggregate ( particle diameter "2.5mm), MC, redispersible powder, air-entraining agents, their weight proportions: gypsum: anhydrite I BU E: water quenched slag: cement: • MC: redispersible plastic Lai Bu entraining agent: sand <table> table see original document page 12 </ column> </ row> <table> ratio above raw materials were weighed, mixed, stirred with water, cement ratio 0.40, casting molding, according to GB / T17671 - 1999 28 days measured bending strength, compressive strength, softening coefficient, adhesion strength was measured according to DIN1168-2, by GB / T1346-2001 measuring clotting time, results in table 3. tABLE 3 strength water bottom paint sample gypsum optimization results final setting time of the initial setting time compression flexural strength Strength of the adhesive strength softening coefficient <table> table see original document page 12 </ column> </ row> <table> Table 3 shows the results of optimization experiments the ratio of the aggregate can be seen: the proportion of aggregates with increasing large, the bending strength of 12 is reduced, the compression strength increases and then decreases, reducing the adhesive strength increases when the ratio of the aggregate to 73.8% (formulation # 29), the construction will be more difficult, so the ratio of aggregate not more than 73.8%. aggregate not added products, such as (a), (b) Example products, particularly suitable for use as a surface layer of paint products with the addition of aggregates, such as (c) Example product embodiment, especially suitable to use as the underlying paint of Example activated attapulgite clay treated (referred activity attapulgite clay) of organic pollutants in the air, formaldehyde, benzene, xylene, ammonia (iv) high-strength water-embodiment plaster Eco , hydrogen sulfide, carbon monoxide has a strong adsorption capacity, activated attapulgite clay was added in the plaster, indoor furniture can adsorb volatile formaldehyde, benzene, ammonia and other harmful gases, such as radon gas, hydrogen sulfide, and carbon monoxide, in order to develop eco-paint stone The original hopper Wo: instead of gypsum dihydrate gypsum (water content 1%, particle size 200 mesh), and more gypsum in place of 5 (200 mesh particle size) using a anhydrite II S, active admixture is ground water quenched slag, alkaline activator to 325 # cement coagulant, alum (100 mesh size), the activity of the adsorbent is attapulgite clay, Mc, redispersible powder, the weight ratio of each component material: gypsum: anhydrite II-S: water quenched slag: cement: Ming fan: the MC: redispersible plastic color}: active attapulgite 43.6 * 40: 20:: 273: 9.1: 3.0: 0.1 : 1.0: 041 * 'two 43.6: 20 -: 27.3: 9.1: 3.0: 0.1: 1.0: 3.042 * = 43.6: 20:: 27.3: 9.1: 3.0: 0, 1: 1.0! : 10.043 * = 43 6:. 20: 27.3 9. 1: 3.0: 0. 1: 1.0: 15.044s = 43 6:. 20:: 27 3:. 9. 1: 3.0: 0. 1: 1.0: 20.045 * = 43.6: 20: 27.3: 9.1: 3.0: 0.1: 1.0: 15 (diatomaceous earth) in the above proportion, the raw materials were weighed, mixed, stirred with water, cement ratio 0.35, casting molding, die size: 40X40X160 training, according to GB / T17671-1999 measured 28 days bending, compressive strength, and wet strength was measured 72 hours soaked in water ( Softening coefficient calculation), the experimental results shown in Table 4 :( Continued) Table 4 results Eco plaster samples the mechanical properties of flexural strength MPa Compressive strength MPa Remarks softening coefficient% 40 * 3.6 38.3 0. 85 41s 3,2 36.2 0.85 2.8 22.2 0.82 42 # 43 # 44 * 2.6 1.2 0.82 9.0 0.82 1,6 significantly prolonged curing # 45 2.5 15.6 0.82 the results in table 4 mechanical properties of plaster ecological, it can be seen as attapulgite clay content increases, the mechanical properties of plaster significantly reduced, particularly when the weight fraction of attapulgite reached 16.1%, the compressive strength was reduced to 9. 0Mpa, instead of attapulgite clay with diatomaceous earth also similar properties, the weight fraction of gypsum plaster in the eco-based composite cementitious material is greater than 2%, less than 16.1%, the activity of attapulgite clay or diatomaceous earth may be added to the base layer and the surface layer stucco gypsum , indoor harmful gas adsorption, improve indoor air quality.

Claims (10)

1. A high-strength water-resistant gypsum stucco, wherein the weight ratio of the composition of the following materials: gypsum 10% to 99% based composite cementitious material, aggregate 0 to 90%, additives 0.08 to 4%, the adsorbent 0 to 16.1%; the gypsum binder based composite material consists of the following components: mixing gypsum powder, 40% to 80%, active admixture of 10% to 45%, 4% alkaline activator to 15%, can redispersible powder from 0.1% to 2%, coagulant 0% to 6%, 0 to 5% lime, early strength agent 0 ~ 1%, water-reducing agent 0 to 1%, 0 to 1.0% fibers; the mixture gypsum plaster powder selected from powder a powder anhydrite or mixtures thereof; said gypsum powder is natural gypsum powder, gypsum powder, gypsum powder pretreated or pretreated phosphorus lemon gypsum powder, powder size 60 mesh to 500 mesh; the anhydrite gypsum is finely ground fluoro, direct grinding of anhydrite II anhydrous gypsum or calcined gypsum dihydrate 360 ​​~ 1000 deg.] C is formed, which comprises 360 to 500 slow firing ℃ soluble anhydrite formed II-S, insoluble anhydrite 500 ~ 700 ℃ calcined form II-U, 700 ~ 1000 ℃ fumed Pouring burning anhydrite II-E is formed; fluoro-gypsum, anhydrite II-S, II-E anhydrite particle size of 80 to 300 mesh, natural anhydrite, anhydrite II-U a particle size of 100 to 500 mesh; the active powder is selected from ground water quenched slag, pulverized fly ash, ground slag refining iron, iron alloy ground slag, silicon lithium ground slag powder, silica fume, ground Fluorspar one or both of mixtures of the above; the alkaline agent is excited Portland cement, cement, cement, lime, or soda residue carbide slag; the coagulant is selected from Na2SO4, K2SO4, NaHSO4, KHSO4 , CuSO4, FeSO4, AL2 (SO4) 3, ZnSO4, KAL (SO4) 2 · 12H2O), a mixture of K2Cr2O7 one or two or more kinds; coagulant grinding to a particle size of ≥100 mesh; said adsorbent active clay attapulgite; the aggregate is quartz sand and / or limestone powder, particle size less than 4mm; the additive is the MC methylcellulose, air-entraining agents, starch ethers, thixotropic lubricants, defoamers one or a mixture of several kinds.

2, high-strength water-resistant plaster according to claim l, characterized in that the gypsum-based composite cementitious material ratio of 40% ~ 70%, the ratio of the aggregate 30% ~69%.

3, high-strength water-resistant wall plaster of claim 1 or claim 2, characterized in that the gypsum-based composite cementitious material is gypsum powder mixing ratio of 50% ~ 70%, ratio of active admixture 15% to 35%, an alkaline activator ratio is 6% ~ 12%, coagulant ratio of 1% ~ 3%.

4, high-strength water-resistant wall plaster of claim 1 or claim 2, characterized in that the mixing gypsum powder, gypsum: 30% ~ 90% anhydrite two: 10% ~ 70%; gypsum powder 80 mesh ~ 200 mesh; anhydrite fluoro gypsum, anhydrite I1-S, E anhydrite II a particle size of 100~250 mesh, natural anhydrite, anhydrite II is a particle size of 250~400 mesh U .

5, high-strength water according to claim 1 or claim 2, wherein the plaster, characterized in that the mixing gypsum powder further contains 0~15% of hemihydrate gypsum.

6, high-strength water-resistant wall plaster of claim 1 or claim 2, characterized in that the active powder is a water quenched slag and fly ash mix.

7, high-strength water-resistant plaster according to claim 6, wherein said mixture of ash and water quenched slag ratio of fly ash: water quenched slag = 1: i.

8, high-strength water-resistant wall plaster of claim 1 or claim 2, wherein the active clay attapulgite with chabazite, mordenite zeolites, activated carbon, montmorillonite, sepiolite powder, diatomaceous earth one or two or more powder mixture in place.

9, high-strength water-resistant wall plaster of claim 1 or claim 2, wherein said methyl cellulose methyl hydroxyethyl cellulose ether with MC of MHEC, MHPC hydroxypropyl methyl cellulose ethers or hydroxyethyl HEC instead of ethyl cellulose.

10, according to claim one of the high-strength water producing gypsum stucco 1-8, characterized in that the predetermined proportion of the raw materials for weighing and drying the aggregate, and all the ingredients mixed .