A kind of phosphogypsum premixing dry-mixed mortar that can be used for 3D and print
Technical field
The present invention relates to field of mortar, in particular to a kind of phosphogypsum premixing dry-mixed mortar that can be used for 3D and print.
Background technology
Phosphogypsum is that phosphogypsum is a kind of powder material, does not almost have plasticity-with the waste residue produced during sulfuric acid treating phosphorite in phosphoric acid production, and therefore most treatment process all adopts the mode process of accumulation.The bulk deposition of phosphogypsum, has has not only occupied a large amount of land resources, and because reasons such as wind erosion, weathering, causes the pollution of air, water system and soil.How effectively to process phosphogypsum industrial waste, be all at home and abroad problem in the urgent need to address.
In the prior art, someone proposes by phosphogypsum manufacture mortar body of wall component PC component or the method printing overall house, solve the accumulation problem of phosphogypsum, its principle is that phosphogypsum is identical with plaster of paris chemical composition, crystal habit is similar, and the content of CaO is greater than 30%, and containing a small amount of free phosphoric acid, fluorine and organism, therefore, phosphogypsum can use as the starting material of material of construction body of wall or house.
The gypsum premixing dry-mixed mortar that traditional processing technology is made into, have an obviously defect, namely ultimate compression strength is very low.The ultimate compression strength of the gypsum premixing mortar adopting conventional gypsum making method to make generally only has about 4.5, in constructions work, can only be used for partition wall or filled wall, can not use as bearing wall.And traditional gypsum premixing dry-mixed mortar, be limited to the shortcoming that gypsum is not water-fast, the non-constant of water tolerance, therefore, traditional gypsum premixing dry-mixed mortar can't use as outer wall material, further limit the application adopting industrial phosphogypsum to make construction material.
Further, conventional gypsum premixing dry-mixed mortar is limited to the reasons such as mortar physicochemical property, in Specific construction link, artificial construction can only be adopted, because the physical and chemical parameter such as viscosity, initial set, final setting time of traditional gypsum premixing dry-mixed mortar does not reach requirement, cannot be applied to 3D printer device people, the overall house of field print or body of wall component PC component, greatly limit its application.
Summary of the invention
The object of the present invention is to provide a kind of phosphogypsum premixing dry-mixed mortar that can be used for 3D and print, described can be used for 3D print phosphogypsum premixing dry-mixed mortar ultimate compression strength high, water resistance is good, both can use as interior wall material after laminating production, can use as outer wall material again, and can bearing wall be used for, 3D printing technique can be adopted to print overall house or body of wall component PC component assembling construction.
In order to realize above-mentioned purpose of the present invention, spy by the following technical solutions:
Can be used for the phosphogypsum premixing dry-mixed mortar that 3D prints, comprise following composition: by weight, dihydrate gypsum 500-600 part, aggregate 400-500 part, coal ash 30-50 part, redispersable latex powder 0.2-0.8 part, whipping agent 0.2-0.3 part, retardant 1-1.5 part, water-holding agent 0.5-0.7 part.
The solid materials of the phosphogypsum premixing dry-mixed mortar that the above-mentioned 3D of can be used for prints is made up of packing material and composite additive two parts.Wherein, packing material is made up of dihydrate gypsum and aggregate, instead of traditional cement, both gypsum had been recycled, overcome again that cement easily chaps, the problem of hollowing, have, sagging performance be good, ultimate compression strength high (more than 8 MPas), bonding strength is high, water resistance is excellent, be applicable to multiple body of wall (interior wall, exterior wall, bearing wall), fire resistance are good, heat insulating, construction are not subject to seasonal restrictions, can the advantage such as the outer humidity of adjusting ambient automatically; Composite additive is made up of redispersable latex powder, whipping agent, retardant and water-holding agent, for improving the physical and chemical parameters such as the ultimate compression strength of mortar, water tolerance and viscosity, initial set, final setting time, can be used for multiple body of wall, can be used for 3D and print.
Particularly, redispersable latex powder can solve the cementability of mortar and the parcel of aggregate, improves workability, and improve liquidity energy, increases thixotroping and anti-property of hanging down, improves force of cohesion, prolongation open hour and enhancing water-retentivity; Especially the effect in hardened mortar improves mortar tensile strength, strengthens folding strength, reduces Young's modulus, improves deformability, promotes abrasive wear resistance, improves cohesive strength, reduces carbonation depth, reduces material water-absorbent, make material have hydrophobic nature etc.
Whipping agent is got angry in mortar inside, improves mortar workability, improves impervious, the freeze proof and weather resistance of mortar, reduction mortar strength, increases mortar volume.
Retardant is the hydration rate and the hydration heat that reduce phosphogypsum, thus reduces or avoid, because hydration heat too concentrates the crack producing temperature difference pressure and cause, delaying mortar coagulation time, extending the operating time.
Water-holding agent can improve initial set, the final setting time of mortar, makes it be adapted to 3D and prints.
Preferably, described water-holding agent is 1-1.5 part ether of cellulose.Ether of cellulose solves water retentivity of mortar, extend the engineering time, mortar is made to keep sufficient moisture in long-time, water also plays a part lubrication and mix in inorganic composition, fresh mortar thickening can be made, thus prevent segregation, and obtain the plasticity-of uniformity, ether of cellulose itself also has air-entraining effect, can also stablize the even tiny bubble introduced in mortar.Through screening, the ether of cellulose modified effect of the 200000 above viscosity of unit is good.
Preferably, also comprise lagging material, described lagging material select following in one or more: glass microballon, perlite, granular polystyrene.These materials have excellent fire resistance and heat-insulating property, are suitable for building thermal insulation material field.
Preferably, described solid materials also comprises promoting agent.Promoting agent is that to solve mortar active, avoids later stage dry linting, retardant is the hydration rate and the hydration heat that reduce cement or phosphogypsum, extend a kind of additive of time of coagulation.·····
Preferably, described whipping agent is one or more in k-12 sodium lauryl sulphate, dichloro tetrafluoro ethane and Refrigerant 12.Wherein, k-12 sodium lauryl sulphate is prioritizing selection, and it not only has foaming effect, also has activation, can solve the problem of mortar later stage dry linting.
Preferably, described retardant is trimeric cyanamide, and/or citric acid.Because citric acid is along with the increase of addition, clearly, trimeric cyanamide is then relatively slow in gypsum loss of strength, and therefore, as preferably, the preferred trimeric cyanamide of the present invention is as retardant.
Preferably, described redispersable latex powder is neutral redispersable latex powder, and/or flexible redispersable latex powder.Wherein, the anti-contracility of flexible redispersable latex powder is stronger, and the anti-contracility deviation of neutral polymer dispersion powder, but the anti-extension ability of neutral polymer dispersion powder is better with the property pasted, therefore as preferred, the preferred neutral polymer dispersion powder of the present invention: the ratio of flexible polymer dispersion powder is 0.8-1.2:2 (weight ratio), more preferably 1:2.
Preferably, described aggregate is coarse whiting, and/or fine sand and/or phosphorus slag and/or building waste.
Preferably, also comprise 1.8-2.2 part polycarboxylate high performance water-reducing agent, preferably 2 parts.
Add polycarboxylate high performance water-reducing agent and the ultimate compression strength of mortar can be improved 20%-50%, make ultimate compression strength reach more than 10 MPas.
Preferably, also comprise: 50-80 part cement.
For increase phosphogypsum premixing dry-mixed mortar solidify after later strength, can in major ingredient of the present invention, a certain proportion of cement, after adding cement and increasing mortar later stage setting strength further, the intensity of phosphogypsum premixing dry-mixed mortar of the present invention can reach more than 11 MPas.
Preferably, with steel construction and attached rack connected applications.
Bearing wall structure is realized for real meaning, can on basis of the present invention, be combined with nonspecific steel construction and attached rack, connected applications is wrapped up by steel construction and attached rack and phosphogypsum premixing dry-mixed mortar, further increase spray body of wall house later strength, house/strength of wall body that phosphogypsum premixing premixing mortar of the present invention and steel construction and attached rack wrap up connected applications can reach more than 35 MPas.
Dihydrate gypsum preferably adopts following methods to obtain: in inert gas atmosphere, phosphogypsum is calcined 1-5h under 900-1100 DEG C of flue-gas temperature, obtains product.Compared with prior art, the calcining temperature that this preparation method adopts is high, and calcination time is long, thus the water gypsum in phosphogypsum and dihydrate gypsum reaction can be made to be converted into dihydrate gypsum, makes the dihydrate gypsum of generation form β type crystal habit, makes P
2o
5that impurity resolves into gas or is partially converted to inertia, stable insoluble phosphorus acid compounds (as Calcium Pyrophosphate), thus it is reduced to lower-most point to the harm of product performance, a small amount of organophosphorus is made to become gas to discharge through high temperature transformation, inorganic phosphorus is combined into the Calcium Pyrophosphate of inertia at high operating temperatures with calcium, thus eliminates the harm of the impurity such as organophosphorus and inorganic phosphorus to gypsum performance.
Certainly, the preparation method of dihydrate gypsum can improve again, such as: be placed at by phosphogypsum in the calcining kiln of nitrogen atmosphere, within 30min, flue-gas temperature is warming up to 950 DEG C, calcine 1h at this temperature, then within 20min, flue-gas temperature is warming up to 1050 DEG C, calcine 4h at this temperature; Phosphogypsum after calcining is naturally cooled to 25 DEG C, then places 2 days in atmosphere.Greatly can improve the ultimate compression strength of dihydrate gypsum, water resistance and setting and harden speed like this.
Compared with prior art, beneficial effect of the present invention is:
(1) a kind of phosphogypsum premixing dry-mixed mortar that can be used for 3D printing of excellent performance is developed, it can coordinate 3D printer device people to use, namely with computer, building structure is programmed, the running orbit of this time variable control 3D printing device, spray phosphogypsum premixing dry-mixed mortar of the present invention, a house can be gone out or body of wall component PC builds by printing speed, overturn traditional building operation industry.
(2) solve the problem such as dry linting, waterproof by the modification of additive, during for surface decoration, metope densification is smooth and do not play ash, has higher intensity and does not shrink, outward appearance elegance, odorlessness, flawless.
(3) ultimate compression strength is up to more than 8 MPas, and water resistance is good, and the fragment of brick made with it soaks after one month unchanged in water.
(4) extending can the engineering time.
(5) construction is not subject to seasonal restrictions: when especially winter, (more than-5 DEG C) tried to meet the deadline for the project, the untired temperature of its hydration rate is low and obviously slow down, as long as mixing water does not freeze, namely having early strong fast solidifying characteristic, is the good material of indoor plastering construction in winter.
(6) have that sagging performance is good, bonding strength is high, be applicable to the advantages such as multiple body of wall.
(7) curing cycle is short: the presetting period is short, greatly can increase work efficiency, speed up the work.
(8) can the outer humidity of adjusting ambient automatically: dihydrate gypsum belongs to a kind of porous material, is conducive to automatic surge chamber humidity, when indoor humidity is larger, breathes automatic moisture absorption; Under contrary condition, automatically can discharge the moisture of deposit, iterative cycles, indoor humidity be controlled within optimum range, for occupant creates good living environment.
(9) fire resistance is good: dihydrate gypsum belongs to inorganic materials, have not so property, when presence of fire, dihydrate gypsum hardenite has mass crystallization water to discharge under heat effect, form steam, block spreading of flame, simultaneously in the heat that whole dehydration middle rank is sent out a large amount of, thus improve the safety that resistivity against fire effectively ensures building.
(10) thermal and insulating performance is good: dihydrate gypsum hardenite is a kind of porous material, and thermal conductivity is little, and thermal and insulating performance is good.
(11) good workability: after scene adds water and stirs, directly upper wall is plastered without the need to using interfacial agents, and construction expanded area is large, when site environment is feasible, can adopt mechanically spraying, wall surface levelling place can thin limed construction; The thinlyyest do to 0.5 centimeter, labor and material saving saves time.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting the scope of the invention.Unreceipted actual conditions person in embodiment, the condition of conveniently conditioned disjunction manufacturers suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, be and can buy by commercially available the conventional products obtained.
It is as shown in table 1 that aggregate grade in Examples below 1-10,12-16 joins district, the character of the dihydrate gypsum of all embodiments is as shown in table 2, and the redispersable latex powder of the neutrality that all embodiments relate to or flexibility all refers to EAV (ethylene-vinyl acetate copolymer) latex powder.
Table 1 aggregate grade joins district
|
Ith district |
IIth district |
IIIth district |
5.00mm |
10-0 |
10-0 |
10-0 |
2.5mm |
35-5 |
25-0 |
15-0 |
1.25mm |
65-35 |
50-10 |
25-0 |
0.63mm |
85-71 |
70-41 |
40-16 |
0.315mm |
95-80 |
92-70 |
85-55 |
0.16mm |
100-90 |
100-90 |
100-90 |
The character of table 2 dihydrate gypsum
Dihydrate gypsum moisture % |
25 |
The water-soluble unicorn % of dihydrate gypsum |
0.61 |
The insoluble unicorn % of dihydrate gypsum |
0.68 |
PH value |
Approximate 2.5 |
Dihydrate gypsum mobility (amount of water 2:1) |
Better |
Cake pH value is considered in the punching of 50ml water |
4-5 (filtrate is about 3) |
Embodiment 1
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, redispersable latex powder (neutrality mixes with 1:2 weight ratio with flexibility) 0.2 part, k-120.2 part, trimeric cyanamide 1 part, viscosity is the ether of cellulose 0.5 part of 200,000 units.
Embodiment 2
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 600 parts, 500 parts, aggregate, coal ash 50 parts, redispersable latex powder (neutrality mixes with 1:2 weight ratio with flexibility) 0.8 part, k-120.3 part, trimeric cyanamide 1.5 parts, viscosity is the ether of cellulose 0.7 part of 200,000 units.
Embodiment 3
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, redispersable latex powder (neutrality mixes with 1:2 weight ratio with flexibility) 0.5 part, k-120.2 part, trimeric cyanamide 1.3 parts, viscosity is the ether of cellulose 0.6 part of 200,000 units.
Embodiment 4
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, redispersable latex powder (neutrality mixes with 1:2 weight ratio with flexibility) 0.2 part, k-120.2 part, trimeric cyanamide 1 part, viscosity is the ether of cellulose 0.5 part of 250,000 units.
Embodiment 5
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, redispersable latex powder (neutrality mixes with 1:2 weight ratio with flexibility) 0.2 part, dichloro tetrafluoro ethane 0.2 part, trimeric cyanamide 1 part, viscosity is the ether of cellulose 0.5 part of 200,000 units.
Embodiment 6
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, redispersable latex powder (neutrality mixes with 1:2 weight ratio with flexibility) 0.2 part, Refrigerant 12 0.2 part, trimeric cyanamide 1 part, viscosity is the ether of cellulose 0.5 part of 200,000 units.
Embodiment 7
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, redispersable latex powder (neutrality mixes with 1:2 weight ratio with flexibility) 0.2 part, k-120.2 part, citric acid 1 part, viscosity is the ether of cellulose 0.5 part of 200,000 units.
Embodiment 8
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, flexible redispersable latex powder 0.2 part, k-120.2 part, trimeric cyanamide 1 part, viscosity is the ether of cellulose 0.5 part of 200,000 units.
Embodiment 9
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, redispersable latex powder (neutrality mixes with 0.8:2 weight ratio with flexibility) 0.2 part, k-120.2 part, trimeric cyanamide 1 part, viscosity is the ether of cellulose 0.5 part of 200,000 units.
Embodiment 10
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, redispersable latex powder (neutrality mixes with 1.2:2 weight ratio with flexibility) 0.2 part, k-120.2 part, trimeric cyanamide 1 part, viscosity is the ether of cellulose 0.5 part of 200,000 units.
Embodiment 11
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, coarse whiting 400 parts, coal ash 30 parts, redispersable latex powder (neutrality mixes with 1:2 weight ratio with flexibility) 0.2 part, k-120.2 part, trimeric cyanamide 1 part, viscosity is the ether of cellulose 0.5 part of 200,000 units.
Embodiment 12
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, redispersable latex powder (neutrality mixes with 1:2 weight ratio with flexibility) 0.2 part, k-120.2 part, trimeric cyanamide 1 part, viscosity is the ether of cellulose 0.5 part of 200,000 units, 1.8 parts of polycarboxylate high performance water-reducing agents.
Embodiment 13
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, redispersable latex powder (neutrality mixes with 1:2 weight ratio with flexibility) 0.2 part, k-120.2 part, trimeric cyanamide 1 part, viscosity is the ether of cellulose 0.5 part of 200,000 units, 2.2 parts of polycarboxylate high performance water-reducing agents.
Embodiment 14
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, redispersable latex powder (neutrality mixes with 1:2 weight ratio with flexibility) 0.2 part, k-120.2 part, trimeric cyanamide 1 part, viscosity is the ether of cellulose 0.5 part of 200,000 units, 2 parts of polycarboxylate high performance water-reducing agents.
Embodiment 15
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, redispersable latex powder (neutrality mixes with 1:2 weight ratio with flexibility) 0.2 part, k-120.2 part, trimeric cyanamide 1 part, viscosity is the ether of cellulose 0.5 part of 200,000 units, 2 parts of polycarboxylate high performance water-reducing agents, 50 parts of cement.
Embodiment 16
The phosphogypsum premixing dry-mixed mortar that a kind of 3D of can be used for prints comprises: by weight, dihydrate gypsum 500 parts, 400 parts, aggregate, coal ash 30 parts, redispersable latex powder (neutrality mixes with 1:2 weight ratio with flexibility) 0.2 part, k-120.2 part, trimeric cyanamide 1 part, viscosity is the ether of cellulose 0.5 part of 200,000 units, 2 parts of polycarboxylate high performance water-reducing agents, 80 parts of cement.
Experimental example
Adopt 3D printer device people, build fragment of brick with the mortar of above embodiment, investigate its performance, result is as shown in table 3.
Table 3 can be used for the performance of the phosphogypsum premixing dry-mixed mortar that 3D prints
As can be seen from above test completely, phosphogypsum premixing dry-mixed mortar of the present invention solves the problem that gypsum meets the easy dry linting of water, and anti-extension ability is stronger.
Although illustrate and describe the present invention with specific embodiment, however it will be appreciated that can to make when not deviating from the spirit and scope of the present invention many other change and amendment.Therefore, this means to comprise all such changes and modifications belonged in the scope of the invention in the following claims.