CN107098612A - A kind of magnesium system oxalic acid salt cement - Google Patents

A kind of magnesium system oxalic acid salt cement Download PDF

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Publication number
CN107098612A
CN107098612A CN201710255367.1A CN201710255367A CN107098612A CN 107098612 A CN107098612 A CN 107098612A CN 201710255367 A CN201710255367 A CN 201710255367A CN 107098612 A CN107098612 A CN 107098612A
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parts
oxalic acid
magnesia
magnesium system
acid salt
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CN201710255367.1A
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CN107098612B (en
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周新涛
王敬冬
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B9/00Magnesium cements or similar cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B9/00Magnesium cements or similar cements
    • C04B9/02Magnesium cements containing chlorides, e.g. Sorel cement

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Dental Preparations (AREA)

Abstract

The invention discloses a kind of new magnesium system oxalic acid salt cement and preparation method thereof, belong to building material technical field;The binder materials by following weight parts raw material it is well mixed after be made:100 parts of acidic components, 60 150 parts of magnesia adjusts 7 30 parts of gel material, 30 75 parts of water is in parts by weight;The present invention has:Rate of set is controllable, setting time 6min 240min, and hardening is fast, and intensity is high, and cohesive force is strong, and volume stability is good, the advantages of wearability, frost resistance are good;Preparation process of the present invention is simple to operate, can workability it is good, can apply highway, airfield runway, bridge, major trunk roads Rapid-Repair, in Solid Waste Treatment with also having broad application prospects in terms of solidifying.

Description

A kind of magnesium system oxalic acid salt cement
Technical field
The present invention relates to a kind of magnesium system oxalic acid salt cement, belong to building material technical field.
Background technology
Magnesium system soda acid cement, is that a kind of formed by magnesia and acid or acid salt progress acid-base reaction has bonding with one kind The inorganic coagulation material of performance.The more maturation of research at present is magnesium phosphate cement.Also referred to as magnesium phosphate chemically bonded ceramics are gelled Material.Magnesium phosphate be chemically bonded material by the acid phosphate in raw material and magnesia occur chemical reaction form guanite and Produce the binder materials of intensity.Magnesium phosphate cement has than conventional cement better performance at many aspects, for example:It is fast solidifying fast Firmly, early strength is high, and cryogenic temperature condensation speed is fast, and the adhesive strength with old concrete is high;Wearability and frost resistance are good, and drying shrinkage is small. Magnesium phosphate cement has unique performance, highway, airfield runway, major trunk roads Rapid-Repair, Solid Waste Treatment with Had broad application prospects in terms of solidification.
But magnesium phosphate cement is swift in response at high temperature, too fast, again not rapid enough under extremely low temperature, difficulty of construction is hardened Higher, magnesia can release the ammonia with penetrating odor with the reaction of phosphoric acid hydrogen amine, limit it extensive at many aspects Application.Meanwhile, as magnesia oxychloride cement and magnesium oxysulfide concrete industry can be released with penetrating odor gas during the course of the reaction, make Into secondary pollution.
The content of the invention
The present invention is intended to provide a kind of magnesium system oxalic acid salt cement, its constituent and parts by weight are:100 parts of acidic components, oxygen Change 60-150 parts of magnesium, adjust 7-30 parts of gel material.
The water of 30-75 parts of addition when using.
Magnesium system oxalic acid salt cement is by magnesia and the acidic components rich in oxalate react and form a kind of binder materials.It is right The activity of magnesia is not only reduced by high temperature dead burned magnesia in raw material, reaction speed is reduced;Also pass through binoxalate, grass The compounding of acid and oxalates changes pH value to change acidity, changes reaction speed;Add various dose, the adjustable solidification agent of different ratio Change reaction speed;Realize the adjustability of reaction speed.The gas with penetrating odor will not be released during simultaneous reactions, It is more environmentally friendly to environment, so largely widen the application prospect of this material.
Then magnesia of the present invention cross 80 mesh sieves, screen over-size is small by high temperature 900 DEG C of -1500 DEG C of sintering, grindings In 5%.
Acidic components of the present invention are two oxalic acid hydrates, potassium binoxalate, one kind of sodium oxalate or any than several.
It is of the present invention to adjust gel material to be one kind or any than several in borax, boric acid, citric acid, sodium chloride.
The use step of above-mentioned magnesium system oxalic acid salt cement is:
Weigh the raw material of following parts by weight:100 parts of acidic components, 60-150 parts of magnesia, 7-30 parts of gel material of tune, water 30-75 Part;Raw material is mixed, slurry is prepared into.The slurry of gained is poured into rapidly in six gang moulds tool, and vibrated on a vibration table Shaping, upper surface is struck off, and is conserved in natural environment, and magnesium oxalate chemical bonding material solidification body is made;5 after firming body shaping Hour demoulding, conserves certain age using natural curing mode and can be used.
The present invention can improve the micro- of magnesium system oxalates binder materials in its setting time of 6min-240min flexible modulations Architectural characteristic is seen, its strength and stability is greatly improved.This material can be applied in highway, airfield runway, bridge, trunk The Rapid-Repair in road, also has broad application prospects in terms of Solid Waste Treatment with solidification.
Advantage and beneficial effect of the present invention:
(1)Magnesium system oxalic acid salt cement application method of the present invention is similar with cement-based material, and scene need to only add water, and grasps Make simple;Acid-base neutralization reaction generation magnesium oxalate difficulty soluble salt occurs for simultaneous oxidation magnesium and two oxalic acid hydrates or its esters, and be gelled material Material is linked together by way of chemical bonding, binder materials is had certain intensity;
(2)The preparation of magnesium system oxalic acid salt cement of the present invention, binoxalate and two oxalic acid hydrates and oxalates are answered With regulation pH so as to reaction speed, adjust the setting time of binder materials;Setting time extends, difficulty of construction drop Low, binder materials of the invention is more widely used;
(3)Magnesium system oxalic acid salt cement of the present invention releases ammonia, chlorine oxygen magnesium water compared with ammonium magnesium phosphate cement during the course of the reaction Mud releases chlorine, and magnesium oxysulfide concrete is released sulfur dioxide gas and compared, and the material will not release the gas with penetrating odor, Environmental protection, does not result in secondary environmental pollution;
(4)Magnesium system oxalic acid salt cement of the present invention not only possesses magnesium system phosphate concrete intensity height, and cohesive force is strong, body Product stability is good, and the material is with can rapid condensation, intensity under extremely low temperature with traditional inorganic ceramic binder materials compared with It is higher, the advantages of compatibility between old concrete is good, wearability is good, frost resistance is good;And it is adjustable to realize reaction speed.
Brief description of the drawings
Fig. 1 is the magnesium system oxalate chemical bonding material SEM of embodiment 3 figures;
Fig. 2 is the magnesium system oxalate chemical bonding material XRD of embodiment 3.
Embodiment
The present invention is described in further detail below in conjunction with drawings and examples, but the scope of the present invention is not limited to The content.
Embodiment 1:This magnesium system oxalates cement composition thing is:Acidic components 100g, magnesia 100g, tune gel material 12g Part;Wherein acidic components are potassium binoxalate;Magnesia crosses 80 mesh sieves after 1500 DEG C sinter, and screen over-size is not more than 5%;Adjust solidifying Material is boric acid 5g, sodium chloride 5g, sodium citrate 2g, uses water 40g;
Above-mentioned raw materials are mixed evenly, fast pouring enters in 20mm*20mm*20mm six multi pack moulds, on a vibration table Vibration moulding, top is struck off, and determines its setting time for 15min, after 5 hours the demoulding and in atmosphere natural curing to certain Age, test its mechanical property:1d, 3d, 7d compression strength are respectively 32.52Mpa, 33.33Mp, 33.87Mpa.
Embodiment 2:This magnesium system oxalates cement composition thing is:Acidic components 100g, magnesia 100g, tune gel material 12g Part;Wherein acidic components are potassium binoxalate;Magnesia crosses 80 mesh sieves after 900 DEG C sinter, and screen over-size is not more than 5%;Adjust solidifying Material is boric acid 5g, sodium chloride 5g, sodium citrate 2g, uses water 40g;
Above-mentioned raw materials are mixed evenly, fast pouring enters in 20mm*20mm*20mm six multi pack moulds, on a vibration table Vibration moulding, top is struck off, and determines its setting time for 13min, and natural curing is to one after being stripped after 5 hours and in atmosphere Fixed age, test its mechanical property:1d, 3d, 7d compression strength are respectively 32.15Mpa, 32.96Mp, 33.02Mpa.
Embodiment 3:This magnesium system oxalates cement composition thing is:Acidic components 100g, magnesia 130g, tune gel material 13g Part;Wherein acidic components are two oxalic acid hydrates;Tune gel material is borax 10g, sodium chloride 3g, uses water 55g;
Above-mentioned raw materials are mixed evenly, Quick pouring enters in 20mm*20mm*20mm six multi pack moulds, on a vibration table Vibration moulding, top is struck off, and determines its setting time for 6min, after 5 hours the demoulding and in atmosphere natural curing to certain Age, test its mechanical property:1d, 3d, 7d compression strength are respectively 31.52Mpa, 32.06Mp, 32.98Mpa.
SEM morphology analysis is carried out to the material, Fig. 1 is as a result seen, firming body combines more close, phase as we can see from the figure Link to form the binder materials with some strength each other between neighbour.There is part needle bar shape unreacted in firming body Magnesia.XRD analysis are carried out to the material, Fig. 2 is as a result seen, it can be seen that reaction has been mainly generated with certain compression strength Oxalic acid dihydrate magnesium, magnesium oxalate, while also unreacted magnesia.
Embodiment 4:This magnesium system oxalates cement composition thing is:Acidic components 100g, magnesia 100g, tune gel material 12g Part;Wherein acidic components are potassium binoxalate;Magnesia is the chemically pure reagent of unprocessed mistake, and it is boric acid 5g, chlorine to adjust gel material Change sodium 5g, sodium citrate 2g, use water 40g;
Above-mentioned raw materials are mixed evenly, fast pouring enters in 20mm*20mm*20mm six multi pack moulds, on a vibration table Vibration moulding, top is struck off, and determines its setting time for 12min, and natural curing is to one after being stripped after 5 hours and in atmosphere Fixed age, test its mechanical property:1d, 3d, 7d compression strength are respectively 31.15Mpa, 32.08Mp, 32.63Mpa.
Embodiment 5:This magnesium system oxalates cement composition thing is:Acidic components 100g, magnesia 60g, 7g parts of gel material of tune; Wherein acidic components are potassium binoxalate;Magnesia crosses 80 mesh sieves after 1500 DEG C sinter, and screen over-size is not more than 5%;Adjust solidifying material Expect for boric acid 3g, sodium chloride 3g, sodium citrate 1g, to use water 30g;
Above-mentioned raw materials are mixed evenly, fast pouring enters in 20mm*20mm*20mm six multi pack moulds, on a vibration table Vibration moulding, top is struck off, and determines its setting time for 13min, after 5 hours the demoulding and in atmosphere natural curing to certain Age, test its mechanical property:1d, 3d, 7d compression strength are respectively 24.75Mpa, 25.47Mpa, 25.58Mpa.
Embodiment 6:This magnesium system oxalates cement composition thing is:Acidic components 100g, magnesia 150g, tune gel material 18g Part;Wherein acidic components are potassium binoxalate;Magnesia crosses 80 mesh sieves after 1500 DEG C sinter, and screen over-size is not more than 5%;Adjust solidifying Material is boric acid 7.5g, sodium chloride 7.5g, sodium citrate 3g, uses water 50g;
Above-mentioned raw materials are mixed evenly, fast pouring enters in 20mm*20mm*20mm six multi pack moulds, on a vibration table Vibration moulding, top is struck off, and determines its setting time for 11min, and natural curing is to one after being stripped after 5 hours and in atmosphere Fixed age, test its mechanical property:1d, 3d, 7d compression strength are respectively 25.75Mpa, 27.47Mpa, 27.89Mpa.
Embodiment 7:This magnesium system oxalates cement composition thing is:Acidic components 100g, magnesia 100g, tune gel material 12g Part;Wherein acidic components are potassium binoxalate 50g, two oxalic acid hydrate 50g;Magnesia crosses 80 mesh sieves, sieve after 1500 DEG C sinter Surplus is not more than 5%;Tune gel material is boric acid 5g, sodium chloride 5g, sodium citrate 2g, uses water 40g;
Above-mentioned raw materials are mixed evenly, fast pouring enters in 20mm*20mm*20mm six multi pack moulds, on a vibration table Vibration moulding, top is struck off, and determines its setting time for 10min, and natural curing is to one after being stripped after 5 hours and in atmosphere Fixed age, test its mechanical property:1d, 3d, 7d compression strength are respectively 29.52Mpa, 30.35Mp, 31.59Mpa.
Embodiment 8:This magnesium system oxalates cement composition thing is:Acidic components 100g, magnesia 100g, tune gel material 12g Part;Wherein acidic components are potassium binoxalate 50g, sodium oxalate 50g;Magnesia crosses 80 mesh sieves, screen over-size after 1500 DEG C sinter No more than 5%;Tune gel material is boric acid 5g, sodium chloride 5g, sodium citrate 2g, uses water 40g;
Above-mentioned raw materials are mixed evenly, fast pouring enters in 20mm*20mm*20mm six multi pack moulds, on a vibration table Vibration moulding, top is struck off, and determines its setting time for 240min, and natural curing is extremely after being stripped after 5 hours and in atmosphere Certain age, test its mechanical property:1d, 3d, 7d compression strength are respectively 20.75Mpa, 22.47Mpa, 22.89Mpa.
Embodiment 9:This magnesium system oxalates cement composition thing is:Acidic components 100g, magnesia 100g, tune gel material 12g Part;Wherein acidic components are sodium oxalate 50g, two oxalic acid hydrate 50g;Magnesia is crossed 80 mesh sieves, tailed over after 1500 DEG C sinter Amount is not more than 5%;Tune gel material is boric acid 5g, sodium chloride 5g, sodium citrate 2g, uses water 40g;
Above-mentioned raw materials are mixed evenly, fast pouring enters in 20mm*20mm*20mm six multi pack moulds, on a vibration table Vibration moulding, top is struck off, and determines its setting time for 150min, and natural curing is extremely after being stripped after 5 hours and in atmosphere Certain age, test its mechanical property:1d, 3d, 7d compression strength are respectively 22.45pa, 23.33Mp, 24.52Mpa.
Embodiment 10:This magnesium system oxalates cement composition thing is:Acidic components 100g, magnesia 150g, tune gel material 30g Part;Wherein acidic components are potassium binoxalate;Magnesia crosses 80 mesh sieves after 1500 DEG C sinter, and screen over-size is not more than 5%;Adjust solidifying Material is borax;Use water 50g
Above-mentioned raw materials are mixed evenly, fast pouring enters in 20mm*20mm*20mm six multi pack moulds, on a vibration table Vibration moulding, top is struck off, and determines its setting time for 35min, after 5 hours the demoulding and in atmosphere natural curing to certain Age, test its mechanical property:1d, 3d, 7d compression strength are respectively 24.57Mpa, 25.12Mpa, 25.54Mpa.
Embodiment 11:This magnesium system oxalates cement composition thing is:Acidic components 100g, magnesia 150g, tune gel material 30g Part;Wherein acidic components are potassium binoxalate;Magnesia crosses 80 mesh sieves after 1500 DEG C sinter, and screen over-size is not more than 5%;Adjust solidifying Material is boric acid;Use water 75g;
Above-mentioned raw materials are mixed evenly, fast pouring enters in 20mm*20mm*20mm six multi pack moulds, on a vibration table Vibration moulding, top is struck off, and determines its setting time for 45min, after 5 hours the demoulding and in atmosphere natural curing to certain Age, test its mechanical property:1d, 3d, 7d compression strength are respectively 22.45Mpa, 23.79Mpa, 23.68Mpa.
The part more preferably scheme of example discussed above, the simply present invention, those skilled in the art are in the technology of the present invention The variations and alternatives carried out in aspects all should be comprising within the scope of the present invention.

Claims (4)

1. a kind of magnesium system oxalic acid salt cement, it is characterised in that constituent and parts by weight are:100 parts of acidic components, magnesia 60- 150 parts, 7-30 parts of gel material of tune.
2. magnesium system oxalic acid salt cement according to claim 1, it is characterised in that:Magnesia passes through 900 DEG C -1500 DEG C of high temperature Sintering, grinding, then cross 80 mesh sieves, and screen over-size is less than 5%.
3. magnesium system oxalic acid salt cement according to claim 1, it is characterised in that:Acidic components are two oxalic acid hydrates, oxalic acid Hydrogen potassium, one kind of sodium oxalate or any than several.
4. magnesium system oxalic acid salt cement according to claim 1, it is characterised in that:Tune gel material is borax, boric acid, lemon Acid, one kind in sodium chloride or any than several.
CN201710255367.1A 2017-04-19 2017-04-19 Magnesium oxalate cement Active CN107098612B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113713753A (en) * 2021-09-06 2021-11-30 昆明理工大学 Preparation method and application of magnesium oxalate microspheres

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RU2190578C1 (en) * 2001-02-05 2002-10-10 ОАО "ВНИИСТРОМ им. П.П.Будникова" Method for manufacture of hollow granules
CN103011711A (en) * 2012-12-24 2013-04-03 胡中波 Binder for inorganic solid waste and method
CN106007430A (en) * 2016-05-12 2016-10-12 昆明理工大学 Copper-slag-based ferritic oxalate chemical bonded material and application thereof
CN106045351A (en) * 2016-05-30 2016-10-26 昆明理工大学 Water-granulated-slag-based oxalate chemical bonding material and application thereof
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113713753A (en) * 2021-09-06 2021-11-30 昆明理工大学 Preparation method and application of magnesium oxalate microspheres

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