Preparation method of magnesium oxysulfate cementing material handicraft and magnesium oxysulfate cementing material
Technical Field
The invention belongs to the technical field of magnesium artware materials, and particularly relates to a preparation method of a magnesium oxysulfate cementing material artware and a magnesium oxysulfate cementing material adopted by the preparation method.
Background
Products based on magnesium oxychloride cementing materials have related researches at present, and are air-hardening cementing materials with higher strength performance, but the problems of moisture absorption, halogen return and warping deformation are serious, so that the problems are difficult to overcome at present, and particularly the defects are serious in the preparation of artware with decorative effects, so that the attractiveness and the service life of the artware are influenced.
The magnesium oxysulfate cementing material has the advantage of thoroughly solving the problems that the magnesium oxychloride cementing material absorbs moisture and returns halogen, and is easy to warp and deform after absorbing moisture. The product has smooth surface and small color difference. However, the prior magnesium oxysulfate cementing materials are all used as building materials, and the curing mode is complicated. But no proper raw materials are available for preparing handicraft articles without maintenance treatment, including flowerpots and flower beds in greening decoration, various indoor character relief models and doll sculpts.
In addition, China encourages energy conservation and emission reduction, and reduces the emission of waste and environmental harmful substances, so that the industrial waste and the waste mineral products are required to be fully utilized in the magnesium oxysulfate gel material.
Disclosure of Invention
The invention aims to solve the problem that a magnesium oxysulfate cementing material for artware is not prepared properly in the prior art and aims at recycling waste. The artware prepared by the preparation method does not need maintenance, and the apparent density is more than or equal to 0.80 g/cm3(ii) a The water absorption is less than or equal to 20.0 percent; the water content is less than or equal to 12.0 percent; the dissolving-out amount of chloride ions is less than or equal to 3.0 percent, the breaking strength is more than or equal to 6.5MPa, the compressive strength is more than or equal to 30.0MPa, the softening coefficient is more than or equal to 0.8, and the chloride ions are not damaged or cracked after 25 times of freeze-thaw cycles; and the low-grade magnesite and other industrial and agricultural wastes are fully utilized, and the cost of the product is reduced.
One of the purposes of the invention is to provide a preparation method of a magnesium oxysulfate cementing material handicraft, which comprises the following steps:
1) cleaning a mould of the handicraft, and coating a release agent on the inner surface of the mould;
2) weighing magnesium oxysulfate cementing material, firstly preparing magnesium sulfate solution from magnesium sulfate heptahydrate and water, adding fiber and a modifier, uniformly stirring to form mixed slurry, then adding light-burned magnesium oxide powder into the mixed slurry, stirring, finally adding an active filler, crop wastes, a water reducing agent and a defoaming agent, stirring until the slurry is finally uniformly dispersed, and controlling the total preparation time from the addition of the fiber and the modifier to the final uniform dispersion of the slurry to be 8 ~ 10min, wherein the fluidity of the slurry is 160 ~ 190 mm;
3) the slurry is filled into a metering cylinder, and an artwork is manufactured in a mould by adopting a slurry coating and pasting method; after the operation of the coating and pasting method is finished, the surface of the handicraft is polished by using the slurry, so that the surface of the handicraft is smooth and has no cloth leakage; and then demoulding the formed sample and naturally standing and maintaining.
In the preparation method, the raw materials in the step 2) comprise, by weight, 100% of the total amount of 45% ~ 55% of light-burned magnesia powder, 15% ~ 20% of magnesium sulfate heptahydrate, 20% ~ 25% of water, 1% ~ 3% of active filler, 5% ~ 7% of crop waste, 0.5% ~ 2% of an additive and 0.5% ~ 1.5.5% of fibers, wherein the additive comprises a modifier, a water reducer and an antifoaming agent.
In the preparation method, the light-burned magnesia powder is obtained by calcining low-grade magnesite, the composition of the light-burned magnesia powder contains high-content silicon oxide (the content is 6 ~ 8%) and calcium oxide (the content is 4 ~ 6%), the content of magnesium oxide is 75 ~ 85%, the activity is 50 ~ 65%, the fineness is that the residue of a 180-mesh square-hole sieve is not more than 10%, and the high-value efficient utilization of magnesite resources is improved.
In the preparation method, the purity of the magnesium sulfate heptahydrate is 92 ~ 94%, the magnesium sulfate heptahydrate is a byproduct of preparing boric acid from ascharite, and the use of the raw material solves the problem of high value-added utilization of industrial byproducts to a certain extent.
In the preparation method, the active filler is at least one of fly ash, silica fume and slag; the fineness of the powder is required to be more than or equal to 200 meshes, namely the maximum granularity is 200 meshes.
In the preparation method, the crop waste is at least one of rice husks, rice bran and sawdust, and the particle size range of the crop waste is 0.5 ~ 2 mm.
In the preparation method, the fiber length is 5 ~ 10mm, and the fiber comprises glass fiber yarns and broken glass fiber mesh cloth.
In the preparation method, the modifier comprises ~ 20% of gluconic acid, ~ 20% of phosphoric acid, ~ 15% of calcium saccharate and 3535% of calcium chloride, wherein the added amount of the gluconic acid is 15% of the mass of the admixture, the added amount of the calcium saccharate is 5% of ~% of the mass of the admixture, the added amount of the calcium chloride is 25% of ~ 35% of the mass of the admixture, the water reducing agent is a polycarboxylic acid water reducing agent, the added amount of the water reducing agent is 5% of ~ 10% of the mass of the admixture, and the defoaming agent is tributyl phosphate, and the added amount of the defoaming agent is 5% of ~ 10% of the mass of.
In the preparation method, the slurry coating and cloth pasting method in the step 3) is specifically that a layer of slurry is coated in a mold, the thickness of the slurry coating is 2 ~ 3mm, then a glass fiber mesh cloth which is cut and has the same shape as the size of the mold is laid on the layer of slurry, the glass fiber mesh cloth is brushed flat, the slurry of the first layer is made to seep out from meshes of the cloth, the slurry-cloth-slurry method is sequentially carried out until the artware is formed, the time for manufacturing the artware is controlled within 10 minutes, the thickness of each layer of slurry is kept to be the same, and no air bubbles are left on the surface of the artware.
In the preparation method, the slurry in the step 3) is prepared from MgO: MgSO (MgSO)4·7H2O:H2The O is mixed according to the mass ratio of 1: 0.7 ~ 0.8.8: 0.8 ~ 0.9.9.
In the preparation method, the meshes of the glass fiber mesh cloth in the coating and pasting method are more than or equal to 3mm, and the surface density is more than or equal to 100g/m2。
The invention also aims to provide a magnesium oxysulfate cementing material for preparing the artware, which comprises, by weight, 45% of light-burned magnesia powder ~ 55%, 15% of magnesium sulfate heptahydrate ~ 20%, 20% of water ~ 25%, 1% of active filler ~ 3%, 5% of crop waste ~ 7%, 0.5% of additive ~ 2%, and 0.5% of fiber ~ 1.5.5%;
wherein the light-burned magnesia powder has the magnesia content of 75 ~ 85 percent, the silica content of 6 ~ 8 percent, the calcium oxide content of 4 ~ 6 percent, the activity of 50 ~ 65 percent and the fineness of not more than 10 percent after being sieved by a 180-mesh square-hole sieve;
the purity of the magnesium sulfate heptahydrate is 92 ~ 94%;
the active filler is at least one of fly ash, silica fume and slag, and the fineness is more than or equal to 200 meshes;
the crop waste is at least one of rice husks, rice bran and sawdust, and the particle size range is 0.5 ~ 2 mm;
the fiber length is 5 ~ 10mm, and comprises glass fiber filaments and broken glass fiber mesh cloth;
the additive comprises a modifier, a water reducing agent and a defoaming agent, wherein the modifier comprises ~ 20% of gluconic acid, ~ 20% of phosphoric acid, ~ 15% of calcium saccharate and ~ 35% of calcium chloride, the addition of the gluconic acid is 15% of the modifier, the addition of the phosphoric acid is 15% of ~% of the modifier, the addition of the calcium saccharate is 5% of ~% of the modifier, the addition of the calcium chloride is 25% of ~% of the modifier, the water reducing agent is a polycarboxylic acid water reducing agent, the addition of the water reducing agent is 5% of ~ 10% of the modifier, and the defoaming agent is tributyl phosphate, and the addition of the defoaming agent is 5% of ~ 10% of the;
the fluidity of slurry obtained after the magnesium oxysulfate cementing materials are mixed is 160 ~ 190 mm.
The artware prepared by the method and the magnesium oxysulfate cementing material does not need to be maintained, and can be naturally placed after being formed; the apparent density of the handicraft is more than or equal to 0.80 g/cm3The water absorption rate is less than or equal to 20.0 percent, the water content is less than or equal to 12.0 percent, the chloride ion elution amount is less than or equal to 3.0 percent, the breaking strength is more than or equal to 6.5MPa, the compressive strength is more than or equal to 30.0MPa, the softening coefficient is more than or equal to 0.8, and the situation of breakage and cracking does not occur after 25 times of freeze-thaw cycles.
Compared with the prior art, the invention has the advantages that:
1. the low-grade magnesite is fully utilized. The magnesite resource in the Anshan city accounts for more than 90 percent of China, the low-grade magnesite accounts for more than one third of the magnesite resource, and the low-grade magnesite is not well developed and utilized at present, so that resource waste and environmental pollution are generated.
2. Fully utilizes industrial wastes. With the increase of energy-saving and environment-friendly requirements, the solid waste discharged by steel enterprises is in urgent need to be developed and utilized. The invention utilizes the magnesium borate ore to prepare the residual by-products of magnesium sulfate heptahydrate and industrial ash, thereby realizing energy conservation, emission reduction and high-value and high-efficiency utilization.
3. Fully utilizes agricultural wastes. The invention utilizes the crop wastes as biomass materials to produce green craft products, and realizes the manufacture of high-end magnesium building material products by using low-end raw materials.
4. The material is suitable for preparing artware, and the prepared artware does not need to be maintained and can be naturally placed after being molded.
Detailed Description
The starting materials used in the following examples are all commercially available.
The light-burned magnesia powder contains 75 ~ 85% of magnesia, 50 ~ 65% of activity, 6 ~ 8% of silica, 4 ~ 6% of calcium oxide and 50 ~ 65% of activity, and the fineness of the light-burned magnesia powder is that the residue of the light-burned magnesia powder passing through a 180-mesh square-hole sieve is not more than 10%;
the purity of the magnesium sulfate heptahydrate is 92 ~ 94%;
the fineness of the active filler is more than or equal to 200 meshes;
the grain size range of the crop wastes is 0.5 ~ 2 mm;
the mesh of the glass fiber mesh cloth is more than or equal to 3mm, and the surface density is more than or equal to 100g/m2;
The glass fiber yarn is a short glass fiber yarn with the length of 5 ~ 10 mm.
Example 1
A doll modeling handicraft of magnesium oxysulfate cementing material comprises the following components in percentage by weight: light-burned magnesia powder: 50%, magnesium sulfate heptahydrate 18%, water: 21% and silica fume: 2% and rice bran: 6.5% and additives: 1.5%, glass fiber: 1 percent; the modifier is gluconic acid: the addition amount is 15% of the additive, and the phosphoric acid: the addition amount is 15% of the additive, and the addition amount is calcium saccharate: the addition amount is 15 percent of the additive and calcium chloride: the addition amount is 35 percent of the additive; the water reducing agent is a polycarboxylic acid water reducing agent, and the addition amount of the water reducing agent is 10 percent of that of the additive; the defoaming agent is tributyl phosphate, and the addition amount of the defoaming agent is 10 percent of that of the additive;
the preparation method of the magnesium oxysulfate cementing material doll modeling handicraft comprises the following steps:
1) cleaning a mold of the doll molding handicraft, and coating a release agent on the inner surface of the mold;
2) weighing raw materials, pouring magnesium sulfate heptahydrate powder into water, stirring for 3min to prepare a magnesium sulfate solution, standing for 24h for later use, adding fibers and a modifier into the magnesium sulfate solution, stirring for 1min ~ 2min, adding light-burned magnesium oxide powder into the magnesium sulfate solution, stirring for 1 ~ 2min to prepare magnesium oxysulfate gel material slurry, sequentially adding an active filler and crop wastes into the magnesium sulfate solution, stirring until the slurry is uniformly dispersed, and ensuring that the final total stirring time is controlled to be 8 ~ 10 min;
3) loading the slurry into a metering cylinder, making a blank of an artwork in a mould by a slurry coating and pasting method, coating a layer of slurry in the mould, wherein the thickness of the slurry coating is 2 ~ 3mm, then spreading a cut glass fiber mesh cloth on the layer of slurry, brushing the slurry with dry hair to enable the slurry of the first layer to seep out of meshes of the cloth, then coating a layer of slurry, sequentially operating by a slurry-cloth-slurry method, totally coating 7 layers of slurry and spreading 6 layers of glass fiber mesh cloth until the blank of the artwork is formed, controlling the time for making the blank of the artwork by the slurry coating and pasting method within 10 minutes, controlling the thickness degree of each layer of slurry to be consistent, keeping the surface of the artwork free of air bubbles, finishing the operation by the slurry coating and pasting method, smoothing the surface of the blank of the artwork by using thin slurry to enable the surface of the artwork to be smooth and free of leakage, and naturally maintaining the surface of the artwork after the mould is removed.
After detection, the artware prepared by the embodiment can reach the following standards: from appearance, no obvious color difference and no cracks appear at 28 days; no moisture absorption, halogen return and frost phenomenon; its apparent density is 1.39g/cm3(ii) a The water absorption rate is 14.3 percent; the water content is 7.5%; the elution amount of chloride ions is less than 3.0 percent; the rupture strength is 9.8MPa in 28 days; the compressive strength is 45 MPa; the softening coefficient is more than 0.8; after 25 times of freeze-thaw cycle, the surface of the material is not damaged or cracked.
Example 2
A figure statue handicraft of magnesium oxysulfate cementing material comprises the following components in parts by weight: light-burned magnesia powder: 50%, magnesium sulfate heptahydrate 18%, water: 21% and silica fume: 2% and fly ash: 1% and rice husk: 5.5%, admixture: 1.5%, glass fiber: 1 percent; the modifier is gluconic acid: the addition amount is 20% of the additive, and the phosphoric acid: the addition amount is 20% of the additive, and the addition amount is calcium saccharate: the addition amount is 15 percent of the additive and calcium chloride: the addition amount is 25 percent of the additive; the water reducing agent is a polycarboxylic acid water reducing agent, and the addition amount of the water reducing agent is 10 percent of that of the additive; the defoaming agent is tributyl phosphate, and the addition amount of the defoaming agent is 10 percent of that of the additive;
the preparation method of the magnesium oxysulfate cementing material handicraft has the same specific steps as example 1.
After detection, the magnesium oxysulfate cementing material handicraft prepared by the embodiment can reach the following standards: from appearance, no obvious color difference and no cracks appear at 28 days; no moisture absorption, halogen return and frost phenomenon; the apparent density of the powder was 1.45g/cm3(ii) a The water absorption rate is 13.5 percent; the water content is 6.9%; the rupture strength is 8.9MPa in 28 days; the compressive strength can reach 43 MPa; after 25 times of freeze-thaw cycle, the surface of the material is not damaged or cracked.
Example 3
The magnesium oxysulfate cementing material handicraft comprises the following components in parts by weight: light-burned magnesia powder: 50%, magnesium sulfate heptahydrate 18%, water: 21% and fly ash: 3%, sawdust: 5.5%, admixture: 1.5%, glass fiber: 1 percent; the modifier is gluconic acid: the addition amount is 18% of the additive, and the phosphoric acid: the addition amount is 18 percent of the additive, and the addition amount is calcium saccharate: the addition amount is 13 percent of the additive and calcium chloride: the addition amount is 33 percent of the additive; the water reducing agent is a polycarboxylic acid water reducing agent, and the addition amount of the water reducing agent is 9 percent of that of the additive; the defoaming agent is tributyl phosphate, and the addition amount of the defoaming agent is 9 percent of that of the additive;
the preparation method of the magnesium oxysulfate cementing material handicraft has the same specific steps as example 1.
After detection, the magnesium oxysulfate cementing material handicraft prepared by the embodiment can reach the following standards: from appearance, no obvious color difference and no cracks appear at 28 days; no moisture absorption, halogen return and frost phenomenon; the apparent density of the powder was 1.47g/cm3(ii) a The water absorption rate is 14.0 percent; the water content is 6.6%; the rupture strength is 9.2MPa in 28 days; the compressive strength can reach 46 MPa; after 25 times of freeze-thaw cycle, the surface of the material is not damaged or cracked.
Comparative example 1
The magnesium oxysulfate cementing material handicraft comprises the following components in parts by weight: light-burned magnesia powder: 52.40%, magnesium sulfate heptahydrate 18.6%, water: 17.50%, silica fume: 2% and rice bran: 6.5% and additives: 1.5%, glass fiber: 1.5 percent. The admixture was the same as in example 1.
The preparation method of the magnesium oxysulfate cementing material handicraft has the same specific steps as example 1.
After curing for 3 days, the magnesium oxysulfate cementing material handicraft prepared by the embodiment is observed to have tiny cracks on the surface, the cracks are obvious after curing for 7 days, and the number of the cracks is obviously increased after curing for 28 days.
Comparative example 2
The magnesium oxysulfate cementing material handicraft comprises the following components in parts by weight: light-burned magnesia powder: 50%, magnesium sulfate heptahydrate 18%, water: 21% and silica fume: 4% and rice bran: 4% of an additive: 1.5%, glass fiber: 1.5 percent. The admixture was the same as in example 1.
The preparation method of the magnesium oxysulfate cementing material handicraft has the same specific steps as example 1.
The fluidity of the magnesium oxysulfate cementing material slurry prepared by the embodiment is 210mm, and the slurry is too thin and cannot be immediately coated on the surface of a mold, so that the molding is difficult and the operation is difficult.
Example 4
The magnesium oxysulfate cementing material handicraft comprises the following components in parts by weight: light-burned magnesia powder: 45%, magnesium sulfate heptahydrate 20%, water: 25% of slag: 1% and rice husk: 3%, sawdust: 4% of an additive: 0.5%, glass fiber: 1.5 percent; the modifier is gluconic acid: the addition amount is 20% of the additive, and the phosphoric acid: the addition amount is 20% of the additive, and the addition amount is calcium saccharate: the addition amount is 15 percent of the additive and calcium chloride: the addition amount is 35 percent of the additive; the water reducing agent is a polycarboxylic acid water reducing agent, and the addition amount of the water reducing agent is 5 percent of that of the additive; the defoaming agent is tributyl phosphate, and the addition amount of the defoaming agent is 5 percent of that of the additive;
the preparation method of the magnesium oxysulfate cementing material handicraft has the same specific steps as example 1.
After detection, the magnesium oxysulfate cementing material handicraft prepared by the embodiment can reach the following standards: from the appearanceIn the above, no obvious color difference and cracks appear in 28 days; no moisture absorption, halogen return and frost phenomenon; the apparent density of the powder was 1.43 g/cm3(ii) a The water absorption rate is 15.4%; the water content is 7.3%; the elution amount of chloride ions is less than 3.0 percent; the rupture strength is 7.6MPa in 28 days; the compressive strength is 40 MPa; the softening coefficient is more than 0.8; after 25 times of freeze-thaw cycle, the surface of the material is not damaged or cracked.
Example 5
The magnesium oxysulfate cementing material handicraft comprises the following components in parts by weight: light-burned magnesia powder: 55%, magnesium sulfate heptahydrate 15%, water: 20% of slag: 2.5%, sawdust: 5% of an additive: 2%, glass fiber: 0.5 percent; the modifier is gluconic acid: the addition amount is 20 percent of the mass of the additive, and the phosphoric acid: the addition amount is 20% of the additive, and the addition amount is calcium saccharate: the addition amount is 5 percent of the additive and calcium chloride: the addition amount is 35 percent of the additive; the water reducing agent is a polycarboxylic acid water reducing agent, and the addition amount of the water reducing agent is 10 percent of that of the additive; the defoaming agent is tributyl phosphate, and the addition amount of the defoaming agent is 10 percent of that of the additive;
the preparation method of the magnesium oxysulfate cementing material handicraft has the same specific steps as example 1.
After detection, the magnesium oxysulfate cementing material handicraft prepared by the embodiment can reach the following standards: from appearance, no obvious color difference and no cracks appear at 28 days; no moisture absorption, halogen return and frost phenomenon; the apparent density of the powder was 1.1g/cm3(ii) a The water absorption rate is 14.8%; the water content is 8.5%; the elution amount of chloride ions is less than 3.0 percent; the rupture strength is 7.6MPa in 28 days; the compressive strength is 38.7 MPa; the softening coefficient is more than 0.8; after 25 times of freeze-thaw cycle, the surface of the material is not damaged or cracked.