CN1034912A - Magnesia oxychloride cement that has excellent water-resistance and magnesite concrete - Google Patents
Magnesia oxychloride cement that has excellent water-resistance and magnesite concrete Download PDFInfo
- Publication number
- CN1034912A CN1034912A CN 88100526 CN88100526A CN1034912A CN 1034912 A CN1034912 A CN 1034912A CN 88100526 CN88100526 CN 88100526 CN 88100526 A CN88100526 A CN 88100526A CN 1034912 A CN1034912 A CN 1034912A
- Authority
- CN
- China
- Prior art keywords
- oxychloride cement
- magnesia oxychloride
- water
- aluminate
- cement
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/30—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing magnesium cements or similar cements
- C04B28/32—Magnesium oxychloride cements, e.g. Sorel cement
Abstract
A kind of magnesia oxychloride cement that has excellent water-resistance and magnesite concrete, its magnesia oxychloride cement is by ferric oxide, magnesium chloride, water and admixture are formed, and admixture is an aluminate, or wustite, or ferro-aluminate.In this magnesia oxychloride cement, mix fillers such as sand, stone, wood chip, glass fibre again and can be made into the fine magnesite concrete products.The present invention has water-tolerant, and the intensity height is produced simply, and cost is low, advantage such as is widely used.
Description
The invention belongs to a kind of magnesia oxychloride cement that has excellent water-resistance.
Magnesia oxychloride cement (MgO-MgCl
2-H
2The O system) be that Sorel is born in invention in 1967 earlier, so also claim " Sorel cement " to refer to: magnesium oxide (or light-burned magnesia), the coagulable hardened mixture that magnesium chloride and water are formed by basal component.
Existing magnesia oxychloride cement is compared with silicate cement, and fast solidifying is arranged, intensity height, advantage such as erosion resistance is better, and heat-insulation and heat-preservation is good.But because this cement and goods poor water resistance thereof, thereby its range of application is very limited, so far known to, the hydrated product water soluble of existing magnesia oxychloride cement, simultaneously, they are exposed in the water, can weaken the bonding force between crystal, so the wet tenacity of this cement and goods thereof is very low.
For many years,, improve its wet tenacity, at present in order to improve the water tolerance of oxychloride cement, adopt applies admixture more, and so-called admixture generally is meant phosphoric acid and phosphoric acid salt, and they join in the magnesia oxychloride cement, improve water tolerance, improved the wet tenacity of cement, reduced cure shrinkage etc.But phosphoric acid and phosphoric acid salt have brought other shortcoming again after adding, as: setting rate is slowed down widely, and dry strength descends to some extent, and cost also increases.Existing known phosphoric acid that was used and phosphatic patent have: United States Patent (USP): 4141744; 4185066 etc.; Day disclosure special permission communique: 59102883 etc., German Patent: 2732577 etc.
Secondly, the admixture of use is carbonate and silicate compound.Carbonate mainly is soluble salt as yellow soda ash, salt of wormwood, and they join in the magnesia oxychloride cement, through adding heat release CO
2With the cement-hydrate reaction, form insoluble carbonate.Though this method can be improved the water tolerance of cement, will be after the cement moulding through Overheating Treatment, cumbersome.And used admixture cost is higher, is unfavorable for using.Silicate generally is soluble salt, as: water glass, the multi-silicate lithium, silicon sol, tetraethyl silicate etc., they mainly play a part hold back agent, slow down magnesian hydrolysis, are beneficial to the formation of stable product.What relate to these patents of invention has: United States Patent (USP) 4312674 etc., day disclosure special permission, JP57188438 etc.
In addition, also have the admixture of some other types, as: tensio-active agent, water-resisting agent is as oils compound, organic polymer emulsion etc., purpose is in order to stop the immersion of water, to reduce water-intake rate, reducing intensity and slow down setting rate but these admixtures meetings are serious.
Though more above-mentioned inventions can improve the water tolerance of magnesia oxychloride cement, what have can improve wet tenacity, and some has seriously slowed down setting rate, some has reduced intensity, improve production cost, some has brought difficulty on technology, thereby is not generally adopted.
The objective of the invention is: apply a kind of new admixture, thereby improve the water tolerance of magnesia oxychloride cement, improve its cement intensity, do not change their production method simultaneously, the not serious setting rate of slowing down does not improve production cost; In addition, adopt this magnesia oxychloride cement that has excellent water-resistance, some fillers of admixture can be made the fine magnesite concrete products, and this product can be widely used.
The present invention is achieved in that a kind of magnesia oxychloride cement that has excellent water-resistance, and is containing magnesium oxide, on the basis of compositions such as magnesium chloride and water, applies a kind of admixture, i.e. aluminate, or wustite, or ferro-aluminate.
The hydration and hardening process that it is believed that magnesia oxychloride cement is Mgcl
26H
2O is at Mg(OH)
2Association process in the alkaline aqueous solution, principal reaction product 5Mg(OH)
2Mgcl
28H
2O and 3Mg(OH)
2Mgcl
28H
2O is the ionic coordination compound.Because chlorion is water-soluble bigger, therefore, cement-hydrate is immersed in the water, chlorion can be dissolved in the water, cause the molten mistake of chlorion, the concentration that has changed the system intermediate ion is long-pending, and hydrated product is disintegrated, reduced producing the main crystalline content of intensity in the cured body, and the wet tenacity of magnesia oxychloride cement is seriously reduced.On the other hand, MgO-Mgcl
2-H
2The reaction product of O is the needle-like crystal that chain molecule is formed, its end of the chain is connected with ionic linkage by chlorion, because chlorion has good affinity to water, thereby when water immerses hardenite inside, seriously weakened the bonding force between crystal, the wet tenacity of magnesia oxychloride cement is descended,, just must change the water-soluble and chlorion of its reaction product and the effect of water so will change the water tolerance of this cement.
For this reason, the present invention is just at magnesia oxychloride cement (MgO-Mgcl
2-H
2O) in the system, add aluminate, or wustite, or ferro-aluminate, can improve its water tolerance from above-mentioned two aspects.Aluminate, wustite and ferro-aluminate all are active compounds, and they itself have the hydraulicity, can form the hydrate crystal with the water reaction.When they at MgO-Mgcl
2-H
2In the O system during aquation, because M-go-Mgcl
2-H
2The hydration reaction of O is a thermopositive reaction, and aluminate or wustite or ferro-aluminate can pass through to absorb hydration heat, with the free sub-Mg(OH in the magnesia oxychloride cement hardenite)
2Effect forms insoluble aluminic acid double salt, or ferrous acid double salt, or iron aluminic acid double salt.On the other hand, aluminate or wustite or ferro-aluminate, also can with chlorion generation coordination chemistry, form a kind of new stable coordination compound, thereby stoped chlorion molten mistake and with the affinity interaction of water, reach the purpose that improves the magnesia oxychloride cement wet tenacity.So from above-mentioned two aspects, the water tolerance of its magnesia oxychloride cement has improved widely, moreover, when adding aluminate or wustite or iron aluminium arsenic salt, also can produce activating oxide, and with MgO reaction, thereby increased magnesia oxychloride cement (MgO-Mgcl
2-H
2The O system) alkalescence has improved magnesia oxychloride cement intensity.
Remove and apply the admixture aluminate, or wustite, or outside the ferro-aluminate, add phosphoric acid and aluminum oxide in a small amount again, Tai-Ace S 150 and aluminum oxide, or trolamine etc., the water tolerance of magnesia oxychloride cement is further improved, because these compounds help the formation of insoluble coordination compound.
Obtain water-tolerant, behind the big magnesia oxychloride cement of intensity, can mix fillers such as sand, stone, wood chip, glass fibre and make magnesite concrete products, be used for building, road, fields such as packing.Clearly, the fine magnesia oxychloride cement has been arranged, its purposes is very extensive.
Below for several embodiment.
In order to make admixture can form more insoluble aluminic acid double salt or ferrous acid double salt or ferro-aluminate, can select CaO and Al
2O
3, or CaO and Fe
2O
3Calcium aluminate that mole ratio is less or calcium ferrite reduce Ca in the hardening of cement body as far as possible
2+Content.Therefore, calcium dialuminate, two ferrous acids, one calcium, monocalcium aluminate and tetracalcium aluminoferrite etc. are more effective admixture.Provide the prescription of several magnesia oxychloride cements below:
Example 1: the mixture of magnesia oxychloride cement and content ratio thereof are:
Magnesia (containing 80%MgO) 100
Magnesium chloride brine (22 ° of Be-31 ° of Be) 70-110
Monocalcium aluminate (CA) 1-20
Water is an amount of
Example 2: in example 1, replace monocalcium aluminate with calcium dialuminate.Its content ratio:
Magnesia (containing 80%MgO) 100
Calcium dialuminate 1-20
Magnesium chloride brine (31 ° of Be) 70-110
Water is an amount of
Example 3: in example 1, replace monocalcium aluminate, its content ratio with C 12 A 7:
Magnesia (containing 80%MgO) 100
Magnesium chloride brine (22 ° of Be-31 ° of Be) 70-110
C 12 A 7 1-20
Water is an amount of
Example 4: in example 1, replace monocalcium aluminate, its content ratio with dicalcium ferrite:
Magnesia (containing 80%MgO) 100
Dicalcium ferrite 1-20
Magnesium chloride brine (31 ° of Be) 70-110
Water is an amount of
Example 5: in example 1, with iron calcium aluminate (as: C
6A
2F, C
6AF
2, C
4AF), its content ratio:
Magnesia (containing 80%MgO) 100
Iron calcium aluminate (C
6A
2F, C
6AF, C
4AF) 1-20
Magnesium chloride brine 70-110
Water is an amount of
Example 6: use by monocalcium aluminate, calcium dialuminate, tricalcium aluminate, mineral such as C 12 A 7 are the high-alumina cement or the aluminate-series cement of main ingredient, replace the single mineral monocalcium aluminate in the example 1, the ratio of its content:
Magnesia (containing 80%MgO) 100
High-alumina cement 1-20
Magnesium chloride brine 70-110
Water is an amount of
Example 7: use by dicalcium ferrite ferro-aluminate (as: C
6A
2F, C
6AF
2, C
4AF etc.) the rich iron cement of essential mineral composition or ferro-aluminate series cement replace the single mineral dicalcium ferrite in the example 4, its content ratio:
Magnesia (containing 80%MgO) 100
Ferro-aluminate cement 1-20
Magnesium chloride brine (31 Be) 70-110
Water is an amount of
Example 8: in example 1～example 7, add phosphoric acid and activated alumina or activated ferric oxide in a small amount again, the water tolerance of magnesia oxychloride cement is further improved, the ratio of its each content:
Magnesia (containing 80%MgO) 100
Aluminate or ferro-aluminate 1～20
Phosphoric acid (85%) 0.5～2
Aluminum oxide or ferric oxide 0～3
Magnesium chloride brine (31 ° of Be) 70～110
Water is an amount of
Example 9: in example 1～example 7, add ferrous sulfate and activated alumina or trolamine in a small amount again, the water tolerance of magnesia oxychloride cement is improved further, the ratio of its content:
Magnesia 100
Aluminate or ferro-aluminate 1～20
Ferrous sulfate 0.5～3
Aluminum oxide or trolamine 0～5
Magnesium chloride brine (31Be) 70～110
Water is an amount of
Compound method is in example 1～example 7: activated magnesia or light-burned magnesia are given with Powdered admixture in a small amount and mix, again with them and magnesium chloride (Mgcl
26H
2O) aqueous solution (22 ° of Be～31 ° Be) mix forms grout, get final product the magnesia oxychloride cement that has excellent water-resistance.If add inert filler again, as sand, stone, wood chip; Or active filler; Become the magnesite concrete as mixs such as talcum powder, ground dolomite, silica flour, glass fibre, casting then, sclerosis has just obtained magnesite concrete products at normal temperatures.Can be widely used in fields such as building, packing.
Effect of the present invention is: (seeing Table 1) by experiment data as can be seen, water tolerance of the present invention improves greatly, its wet tenacity also increases, and the not serious setting rate of slowing down.Compound method of the present invention is simple, does not improve production cost;
Table 1
The existing aluminate that adds adds ferro-aluminate
Flexural strength (MPa) 12.0 11.2 13.3
Coefficient of softening 0.49 0.78 0.81
Ultimate compression strength (MPa) 31.0 30.9 32.1
Coefficient of softening 0.64 0.84 0.85
Weight loss (in the flowing water)-7%-2.1%-1.6%
In addition, adopt this water-fast good magnesia oxychloride cement to add sand, stone or glass fibre again and do filler, the intensity and the coefficient of softening of its magnesite concrete products are taller, and its ultimate compression strength can reach more than the 80MPa, and coefficient of softening can reach about 0.90.
Claims (10)
1, a kind of magnesia oxychloride cement that has excellent water-resistance, its main ingredient comprises magnesium oxide, magnesium chloride, water and admixture etc., it is characterized in that: described admixture is an aluminate.
2, by the described magnesia oxychloride cement of claim 1, it is characterized in that: described aluminate is aluminic acid-calcium.
3, by the described magnesia oxychloride cement of claim 1, it is characterized in that: described aluminate is a calcium dialuminate.
4, by the described magnesia oxychloride cement of claim 1, it is characterized in that: described aluminate is a C 12 A 7.
5, a kind of magnesia oxychloride cement that has excellent water-resistance, its main ingredient comprises magnesium oxide, magnesium chloride, water and admixture etc., it is characterized in that: described admixture is a wustite.
6, by the described magnesia oxychloride cement of claim 5, it is characterized in that: described wustite is a dicalcium ferrite.
7, a kind of magnesia oxychloride cement that has excellent water-resistance, its main ingredient comprises magnesium oxide, magnesium chloride, water and admixture etc., it is characterized in that: described admixture is a ferro-aluminate.
8, by the magnesia oxychloride cement of claim 1～7, it is characterized in that: the phosphoric acid and the aluminum oxide that add trace again.
9, by the magnesia oxychloride cement of claim 1～7, it is characterized in that: add Tai-Ace S 150 and aluminum oxide in a small amount again.
10, the magnesite concrete made of the magnesia oxychloride cement that has excellent water-resistance of a kind of usefulness, it is characterized in that: this magnesite concrete is by the magnesia oxychloride cement that has excellent water-resistance, and fillers such as wood chip, sand, stone, glass fibre are formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100526 CN1010406B (en) | 1988-02-10 | 1988-02-10 | Magnesium oxychoride cement and magnesite concrete of good water-proofness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100526 CN1010406B (en) | 1988-02-10 | 1988-02-10 | Magnesium oxychoride cement and magnesite concrete of good water-proofness |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1034912A true CN1034912A (en) | 1989-08-23 |
| CN1010406B CN1010406B (en) | 1990-11-14 |
Family
ID=4831388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88100526 Expired CN1010406B (en) | 1988-02-10 | 1988-02-10 | Magnesium oxychoride cement and magnesite concrete of good water-proofness |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1010406B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973720A (en) * | 2010-10-18 | 2011-02-16 | 武汉钢铁(集团)公司 | Magnesium oxychloride cement aggregate and preparation method thereof |
| CN102036932A (en) * | 2008-05-20 | 2011-04-27 | 保全研究与技术中心 | Durable magnesium oxychloride cement and process therefor |
| CN102060453A (en) * | 2010-12-14 | 2011-05-18 | 支亮 | Magnesium oxychloride concrete composite powder material and preparation process thereof |
| CN104046378A (en) * | 2013-03-13 | 2014-09-17 | 中国石油天然气股份有限公司 | Preparation method of waterproof iron oxide-based desulfurizer |
| CN104326728A (en) * | 2014-09-04 | 2015-02-04 | 浙江天仁风管有限公司 | Enhanced magnesium oxysulfate cement, and method for making sheets by using cement |
| CN104446647A (en) * | 2014-11-20 | 2015-03-25 | 中国科学院青海盐湖研究所 | Spray process based method for improving water resistance of magnesium oxychloride cement products |
| CN105036578A (en) * | 2015-08-18 | 2015-11-11 | 武桂君 | Magnesium oxychloride cement and manufacturing technique thereof |
| CN105198253A (en) * | 2015-09-28 | 2015-12-30 | 中材高新成都能源技术有限公司 | Novel building cement |
| CN105461282A (en) * | 2015-11-20 | 2016-04-06 | 南京福臻再生资源科技股份有限公司 | Alkaline-magnesium special cement and a preparing method thereof |
| CN110183125A (en) * | 2019-06-15 | 2019-08-30 | 北京林业大学 | A kind of high-strength quick-solidifying, low energy consumption chlorine oxygen magnesium inorganic gel materials and preparation method |
| CN111139993A (en) * | 2019-12-26 | 2020-05-12 | 安徽建筑大学 | Spliced magnesium oxychloride cement composite wood chip plate |
| CN111548035A (en) * | 2020-05-15 | 2020-08-18 | 厦门瑞川复材科技有限公司 | Magnesium oxychloride cement and preparation method thereof |
-
1988
- 1988-02-10 CN CN 88100526 patent/CN1010406B/en not_active Expired
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102036932B (en) * | 2008-05-20 | 2015-04-15 | 保全研究与技术中心 | Durable magnesium oxychloride cement and process therefor |
| CN102036932A (en) * | 2008-05-20 | 2011-04-27 | 保全研究与技术中心 | Durable magnesium oxychloride cement and process therefor |
| CN101973720A (en) * | 2010-10-18 | 2011-02-16 | 武汉钢铁(集团)公司 | Magnesium oxychloride cement aggregate and preparation method thereof |
| CN102060453A (en) * | 2010-12-14 | 2011-05-18 | 支亮 | Magnesium oxychloride concrete composite powder material and preparation process thereof |
| CN104046378A (en) * | 2013-03-13 | 2014-09-17 | 中国石油天然气股份有限公司 | Preparation method of waterproof iron oxide-based desulfurizer |
| CN104046378B (en) * | 2013-03-13 | 2016-02-10 | 中国石油天然气股份有限公司 | The preparation method of the iron oxide based sweetening agent of a kind of water tolerance |
| CN104326728A (en) * | 2014-09-04 | 2015-02-04 | 浙江天仁风管有限公司 | Enhanced magnesium oxysulfate cement, and method for making sheets by using cement |
| CN104446647A (en) * | 2014-11-20 | 2015-03-25 | 中国科学院青海盐湖研究所 | Spray process based method for improving water resistance of magnesium oxychloride cement products |
| CN105036578A (en) * | 2015-08-18 | 2015-11-11 | 武桂君 | Magnesium oxychloride cement and manufacturing technique thereof |
| CN105198253A (en) * | 2015-09-28 | 2015-12-30 | 中材高新成都能源技术有限公司 | Novel building cement |
| CN105461282A (en) * | 2015-11-20 | 2016-04-06 | 南京福臻再生资源科技股份有限公司 | Alkaline-magnesium special cement and a preparing method thereof |
| CN110183125A (en) * | 2019-06-15 | 2019-08-30 | 北京林业大学 | A kind of high-strength quick-solidifying, low energy consumption chlorine oxygen magnesium inorganic gel materials and preparation method |
| CN110183125B (en) * | 2019-06-15 | 2022-03-15 | 北京林业大学 | High-strength quick-setting low-energy-consumption magnesium oxychloride inorganic gel material and preparation method thereof |
| CN111139993A (en) * | 2019-12-26 | 2020-05-12 | 安徽建筑大学 | Spliced magnesium oxychloride cement composite wood chip plate |
| CN111548035A (en) * | 2020-05-15 | 2020-08-18 | 厦门瑞川复材科技有限公司 | Magnesium oxychloride cement and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1010406B (en) | 1990-11-14 |
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