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EP0469002A1 - Verfahren zur eindringung in magnesiumzement eines wasserfestigkeit erzeugenden mittels - Google Patents

Verfahren zur eindringung in magnesiumzement eines wasserfestigkeit erzeugenden mittels

Info

Publication number
EP0469002A1
EP0469002A1 EP90906038A EP90906038A EP0469002A1 EP 0469002 A1 EP0469002 A1 EP 0469002A1 EP 90906038 A EP90906038 A EP 90906038A EP 90906038 A EP90906038 A EP 90906038A EP 0469002 A1 EP0469002 A1 EP 0469002A1
Authority
EP
European Patent Office
Prior art keywords
magnesium
source material
process according
water
phosphatic
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.)
Withdrawn
Application number
EP90906038A
Other languages
English (en)
French (fr)
Other versions
EP0469002A4 (en
Inventor
John Ralston
Roger St. Clair Smart
Alexander Donald Mair
Julianna Csavas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MERZ AUSTRALIA PTY. LTD. - ACN 009 351 722
Original Assignee
MERZ AUSTRALIA PTY Ltd - ACN 009 351 722
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by MERZ AUSTRALIA PTY Ltd - ACN 009 351 722 filed Critical MERZ AUSTRALIA PTY Ltd - ACN 009 351 722
Publication of EP0469002A1 publication Critical patent/EP0469002A1/de
Publication of EP0469002A4 publication Critical patent/EP0469002A4/en
Withdrawn legal-status Critical Current

Links

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
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators or shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/16—Acids or salts thereof containing phosphorus in the anion, e.g. phosphates
    • 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
    • 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
    • C04B28/34—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 cold phosphate binders
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials

Definitions

  • the present invention relates to a process for producing magnesian cementitious materials and particularly, but not essentially to the production of magnesium oxychloride hydrate and magnesium oxysulphate hydrate cementitious compositions often known as Sorel cements.
  • Magnesium cements based on reaction of magnesium oxide with magnesium chloride or sulphate have been known for a long time. Such a cement formed with magnesium chloride, in particular, is commonly known as Sorel cement.
  • This magnesium oxychloride hydrate cement when cured, is generally characterized by the presence of the crystalline compounds 5Mg(0H) 2 .MgCl 2 .8H 2 0 and/or 3Mg(OH) 2 .MgCl 2 .8H«0, the relative proportions of the two compounds depending on the stoichiometry of the cured mixture. Formation of the 5Mg(0H) 2 .MgCl 2 .8H 2 0 compound is generally preferred.
  • magnesium oxychloride hydrate cementitious materials are renowned for their ultimate high strength and for the rapidity with which they attain such strength, but unfortunately suffer severe disadvantages which have discouraged wide use.
  • phosphates or secondary phosphates of calcium, magnesium and other alkaline earth metals, zinc, aluminium and copper US Patents 2,351,641, 4,185,066 and 4,158,570.
  • all of the described phosphates are either aci d or neutral phosphates.
  • a water resistant magnesian cementitious product is pro d uce d b y admixing particulate phosphatic material with a reactive magnesium oxide source material, a magnesium chlori d e and/or magnesium sulphate source material and sufficient water to provide a workable slurry and setting the slurry, and wherein the phosphatic material comprises an insoluble basic, hydroxy and/or fluoro phosphatic minera l material which is activated at least by partial acidulation.
  • insoluble phosphatic mineral material can be readily incorporated into a magnesian cementitious material to promote water resistance and superior long term mechanical properties. This has the advantage of being able to utilize relatively cheap phosphatic source material to improve the physical properties of magnesian cements.
  • insoluble basic, hydroxyphosphate and/or fluorophosphate mineral materials confers no water resistance benefit to the cured cement unless they can be activated.
  • the water solubility of a magnesian cement incorporating such inactivated insoluble mineral materials is in the range 25 to 30%, usually about 27%. Solubility is a measure of percentage weight loss after being subjected to a water treatment.
  • insoluble phosphatic minerals particularly basic, hydroxy- and/or fluoro-phosphates although others may be appropriate, can be achieved by partial acidulation, optionally with a pre-calcining step.
  • the partial acidulation of the phosphatic mineral material may be carried out before, during or after its addition to the cement. After such activation, the presence of the phosphatic material in the cement confers a significantly increased water resistance to the cement of 20% or less, preferably about 10% or less and most preferably about 7% or less.
  • a magnesian cement having a water solubility of the order of 10-20% may be most appropriate as a filler but at lower levels may be readily used in structural situations.
  • the mechanical properties, particularly compression strength may only degrade slightly over extended periods of time, in some cases only b y a maximum in the order of 20 to 25% and commonly 10 to 15% or less.
  • the admixing may generally be performed at ambient or room temperature, but there may be circumstances where it is advantageous to mix at elevated temperatures, and by way of example only attention is directed to the process and product described in International Patent A pplication WO 87/04145, the content of which is incorporated herein by reference, which process and product may be modified in accordance with the present invention.
  • the magnesian cement is produced f rom l ow cost or byproduct magnesium compositions, such as bitterns as a source of magnesium chloride and low gra d e magnesite as a source of magnesium oxide.
  • Bitterns is the residual liquor from the controlled evaporation of seawater. It may not be necessary to provide additional water in the mixture to give the slurry a workable consistency if the source materials comprise sufficient water.
  • the magnesium chloride source material is particulate it is preferably finely divided, with, for example, a particle size of less than about 250 micron.
  • a magnesium carbonate mineral such as magnesite or dolomite can be utilised after calcination at sufficiently low temperatures to provide sufficient reactivity in the resultant MgO.
  • Magnesite is preferably calcined at temperatures of less than about 820°C to retain sufficient surface area and reactivity in the product MgO.
  • Dolomite is preferably part calcined to form MgO and calcite before use.
  • sources of MgO such as calcined brucite or calcined magnesium hydroxide, as can be derived from seawater, or mixtures of any of the above, are also suitable for the practice of the process of the present invention.
  • the magnesium oxide source material is finely divided.
  • a phosphatic material comprising as a major portion calcian hydroxyphosphates and/or fluorophosphates may be used in the preferred embodiment.
  • a composition is found oc ⁇ uring naturally in commercially mined phosphate deposits substantially as the mineral apatite, either fluorapatite Ca 5 (P0.) 3 F, hydroxyapatite Ca 5 (P0 4 ) 3 0H, or as a mixed fluoro-hydroxy derivative.
  • fluorapatite Ca 5 (P0.) 3 F hydroxyapatite Ca 5 (P0 4 ) 3 0H
  • a mixed fluoro-hydroxy derivative or as a mixed fluoro-hydroxy derivative.
  • appreciable substitution of the phosphate by carbonate often occurs in the apatite crystal structure, to give carbonate apatites (francolites); these also are suitable compositions, as are chloro apatites.
  • Another composition which may be used in the preferred embodiment is the waste phosphatic material found occuring naturally as the so-called "leached-zone" phosphates in weathered sedimentary phosphate deposits at locations including Florida (USA), Senegal (West Africa) and Christmas Island (Indian Ocean).
  • This phosphate often a mixture of apatite and hydroxyphosphate minerals such as crandallite and millisite, is a low grade ore which cannot at. present be economically converted to other useful products.
  • Preacidulation of the insoluble phosphatic material is advantageously performed using phosphoric acid, sulphuric acid or a combination of the two.
  • Use of phosphoric acid to activate the insoluble phosphatic material can beneficially provide water resistance and mechanical strength superior or substantially equivalent to that achieved using a greater amount of phosphoric acid alone, without the presence of the insoluble phosphatic material.
  • Use of sulphuric acid to preacidulate the insoluble phosphatic material provides water resistance and mechanical properties essentially equivalent to that obtained using phosphoric acid, beneficially allowing total replacement of expensive phosphoric acid by much cheaper sulphuric acid.
  • the phosphatic material in the mixture may not be preacidulated as specified in the immediately preceding paragraph but acidulated at a later stage when the phosphatic component is already bound within the set cementitious matrix, whereby the cement is immersed briefly in an acidic solution to at least partially acidulate that phosphatic mineral component within, or at least close to the surface of, the cementitious object.
  • acid solutions are phosphoric acid and sulphuric acid.
  • the pre- or post- acidulation of the insoluble phosphate mineral component to provide a cementitious product of increased water resistance is carried out after mildly precalcining the insoluble phosphatic component prior to mixing with the other cement components.
  • Such precalcining may be performed at temperatures in the range of, for example, 300 to 700°C, preferably 450 to 550°C for upto about 3 hours.
  • the insoluble phosphatic component comprises, for example, crystalline calcium aluminium hydroxyphosphates such as crandallite and millisite as in the aforementioned low grade ores, calcination for instance at 500°C with a retention time of one hour has been found sufficient to destroy the
  • This precalcining step benefits the use of acids such as hydrochloric and citric in the acidulation step, acids in which calcium aluminium hydroxyphosphate minerals such as crandallite and millisite are relatively insoluble unless mildly calcined to destroy their crystallinity.
  • Table 1 represents advantageous operating parameters and variables which are presently considered appropriate for the magnesian cement production process using Christmas Island mineral phosphatic material preacidulated with phosphoric acid or sulphuric acid and with optional precalcination of the phosphatic material.
  • Preacidulation acid (g/lOOg MgO):
  • Calcination temperature (°C) 300-850 400-600 Calcination duration (minutes) 0.1-180 15-60
  • Phosphatic mineral component (g/lOOg MgO) 2-100 5-25
  • the stoichiometry of the process is controlled to provide as a major crystalline cementitious phase formed in the hardened cement the magnesium oxychloride hydrate
  • additives and fillers may be incorporated into the cementitious mix prior to setting to increase.water resistance and/or mechanical strength, to provide suitable colouring or texture, to control shrinkage or expansion, to control the rheological properties of the cementitious slurry, or simply to act as inert extenders.
  • Such additives which might be used include, but are not limited to, inorganic and organic fibres, pigments, lignins, lignosulphonates, surfactants and foam promoters, superplasticizers, sawdust, woodchips, bagasse, rice hulls, slags, flyash, talc, silica sand, clays and other aluminosili ⁇ ates.
  • the magnesium chloride source material may be replaced wholly or in part by a magnesium sulphate source material such as epsomite.
  • the magnesian cementitious composition of the present invention may have wide applicability in the building and other industries, and may beneficially be incorporated in many products including foamed insulation panels •and coatings and as a binder in particle- and hard-board compositions.
  • a cementitious slurry was prepared by mixing 125 parts of low grade calcined magnesite, containing 100 parts of MgO, with 78 parts of magnesium ch l ori d e h exa h y d rate plus 35 parts of added water.
  • an acidulated s l urry was prepared from 16.7 parts of Christmas Island C-grade phosphate rock (25.2 wt. % P ⁇ ) and 4.2 parts of phosphoric acid. Water was added (3 parts) to maintain a satis f actory consistency and prevent the mixture f rom b ecom i ng too thick. The acidulated mixture was l e f t f or 15 minutes w i th occasional stirring. Ca l cine d C op l ey magnesite ( 125 parts containing 100 parts MgO), magnesium chloride hexahydrate (78 parts) and further water (32 parts ) were next added to the slurry. Af ter stirring, the cementitious slurry was poured into molds and allowed to set.
  • T wo f urt h er preparations were made in a similar manner without addition of Christmas Islan d phosphate by mixing 125 parts of calcined Copley magnesite, 78 parts o f magnesium chloride hexahydrate and 35 parts o f water. To one of these further preparations, 7 parts of phosphoric acid was additionally incorporated.
  • a sample from that preparation containing no Christmas Island phosphate and no phosphoric acid showed a compressive strength of 50 MPa with no water treatment, but water treatment at 80°C caused an identical sample from the preparation to experience almost total disintegration, with an accompanying weight loss of 30 %.
  • a sample from the preparation containing no Christmas Island phosphate but containing 7 parts of phosphoric acid showed a compressive strength of 37 MPa with no prior water treatment, while a sample from the same preparation after the 80°C water treatment exhibited a compressive strength of 23 MPa and a water solubility of 5.5 %.
  • An acidulated slurry was prepared from 16.7 parts of Christmas Island C-grade phosphate rock (25.2 wt. % P.O,.) and 6.3 parts of 70 % sulphuric acid. Sufficient water was added (6 parts) to prevent the mixture from becoming
  • a compressive strength in excess of 54 MPa was exhibited by a 2 cm cube of this cement with no water treatment, while a water treated sample (as before at 80°C) possessed a compressive strength of 21 MPa after associated dissolution of the sample during the water treatment of 7.3 %.
  • This example illustrates a further aspect of the preferred embodiment of the present invention. It unexpectedly demonstrates that despite the higher water solubility (compared to those cement samples in Example 2 containing phosphoric acid) probably due to leaching of the calcium sulphate formed, a high strength is retained after water* treatment, comparable to that water treated sample in Example 2 wherein phosphoric acid was used alone without mineral phosphate addition.
  • the present example further demonstrates that for equivalent water resistance as quantified by compressive strength retention in the cured cement, sulphuric acid, when used in conjunction with an insoluble phosphate mineral component, can beneficially replace the more expensive phosphoric acid used alone.
  • a premix was prepared by addition of 29.4 parts MgO to 30.6 parts water followed b y selected additions of phosphoric acid (as given in Table 2 ) .
  • the premix was left to stand for 15 minutes a f ter wh i ch 69 parts MgCl 2 .6H 2 0 was added f ollowed by the final 70.6 parts MgO premixed with 3.7 parts silica fume.
  • Solubilities with sulphuric acid are higher than those with phosphoric acid, in part, at least, due to the formation of appreciably soluble calcium sulphate with the forme .
  • Silica fume enhances the water resistance of the cements. A 22% weight loss found with silica fume addition but with no phosphate is lower than the 28% found in control cements. The beneficial effect of silica fume is maintained in phosphate containing cements, with the water resistance contributions apparently substantially additive as seen by comparing the water solubility data of this Example with Examples 2 and 3.
  • Two types of cements were prepared from the high grade calcined magnesite from Kunwarara, Queensland: a water resistant cement containing sand, rock phosphate and phosphoric acid and a control cement containing no additive other than sand.
  • phosphate modified cement For the phosphate modified cement, a dry mix was prepared from 1170 g of finely ground Kunwarara calcined magnesite (calcined 800°C; free MgO 93.5 wt. %) and 5 kg of dry sharp quality building sand in a mixer of commercial design. A premix was separately prepared by adding 50 g phosphoric acid to a slurry of 200 g
  • a control cement was similarly prepared by making a dry mix of 1300 g Kunwarara calcined magnesite and 5 kg of dry sand. To this mix was added 1000 ml of the same magnesium chloride solution. Additional water was added to the slurry as required.
  • the phosphate modified cement exhibited compressive strengths in the dry state of about 59 ⁇ 2 MPa.
  • This example demonstrates a novel method o f incorporating the acidulated phosphate in the cement, whereby the phosphate slurry is converted to a fine dry powder by premixing the slurry with a portion of t h e Mg O used in the cement.
  • This dry premix is a convenient way of storing the acidulated phosphate and allpws it to b e added to the cement mix at a convenient later time.
  • the dry premix could also be added back with the remainder of the MgO, for later mixing with the magnesium chloride.
  • a series of cements were prepared with Christmas Island Grade C phosphate rock from which all the apatitic phosphate component had been removed.
  • the apatite was removed by repeating leaching of the rock with 2.5 molar hydrochloric acid solution, while monitoring the l each process products by X-ray diffraction analysis.
  • the X- ray diffraction analysis showed that all apatite originally present had been removed and that the major crystalline phases present in the leached rock were the ca l c i um a l um i nium hydroxyphosphates, crandallite an d millisite; these had remained undissolved in the leaching step.
  • hal f of the samples prepared incorporated this leached phosphate in the precalcined state; the remaining samples i ncorporated the leached phosphate in an uncalcined state.
  • the calcining step used a one hour t h ermal treatment at 550°C in a muffle furnace.
  • the extracted phosphate roc k was acidulated with either concentrated hydrochloric or 70% su l phuric acids for periods ranging from 5 to 10 minutes.
  • the acidulated phosphate was then mixe d wit h 125 parts o f finely ground calcined Copley magnesite ( containing 100 parts free MgO), 63 parts of Mg C l 2 .6H 20 and a b out 42 parts water.
  • the amounts of extracted phosphate rock and of acid used was systematica l ly varied to b e 12.5 or 25 parts/100 parts free MgO and 4.2 or 12.5 parts/100 parts free MgO, respectively.
  • solubility data showed that water solubility was low if calcined leached phosphate rock was used in the cement, averaging 4.6% and 4.5% weight loss for hydrochloric and sulphuric acid, respectively, as ac id u l ating agent.
  • uncalcined leached phosphate rock the corresponding average weig h t losses were much higher, at 18.7 and 13.4%, respectively. This compares to the 25-30% weight loss experience d in control cements with no phosphate addition.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Detergent Compositions (AREA)
EP19900906038 1989-04-05 1990-04-05 Process for forming water resistant magnesian cement introduction Withdrawn EP0469002A4 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AU3522/89 1989-04-05
AUPJ352289 1989-04-05
AUPJ661689 1989-09-27
AU6616/89 1989-09-27

Publications (2)

Publication Number Publication Date
EP0469002A1 true EP0469002A1 (de) 1992-02-05
EP0469002A4 EP0469002A4 (en) 1992-12-02

Family

ID=25643657

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900906038 Withdrawn EP0469002A4 (en) 1989-04-05 1990-04-05 Process for forming water resistant magnesian cement introduction

Country Status (4)

Country Link
EP (1) EP0469002A4 (de)
CA (1) CA2051414A1 (de)
NZ (1) NZ233232A (de)
WO (1) WO1990011976A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN121107723A (zh) * 2025-11-14 2025-12-12 矿冶科技集团有限公司 一种胶磷矿浮选尾矿制备镁基胶凝材料的方法及镁基胶凝材料

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5645637A (en) * 1994-05-30 1997-07-08 Baran Advanced Materials 94 Ltd. Foamed magnesite cement and articles made therewith
BRPI0107913B1 (pt) 2000-01-27 2016-12-20 Tececo Pty Ltd composição de cimento hidráulico
AU779788C (en) * 2000-01-27 2008-01-03 Tececo Pty Ltd Reactive magnesium oxide cements
US10167231B1 (en) * 2017-11-07 2019-01-01 Jet Products, Llc Process for making ultra stable tile backer board
US12454487B2 (en) 2017-11-07 2025-10-28 Mitek Holdings, Inc. Ultra stable structural laminate
US11117836B2 (en) 2017-11-07 2021-09-14 Mitek Holdings, Inc. Ultra stable structural laminate
WO2022032348A1 (en) * 2020-08-12 2022-02-17 UBIQ Technology Pty Ltd High durability magnesium oxychloride cement
CN114525079B (zh) * 2022-01-19 2023-12-29 北京林业大学 一种无醛阻燃氯氧镁水泥基木材胶黏剂及其制备方法

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Publication number Priority date Publication date Assignee Title
US2391493A (en) * 1942-04-21 1945-12-25 Titanium Alloy Mfg Co Quick setting cement
US4352694A (en) * 1980-07-18 1982-10-05 Norcem A.S. Process of producing sorel cement
CA1277342C (en) * 1985-05-20 1990-12-04 Fawzy G. Sherif Fast-setting cements from ammonium phosphate fertilizer solution

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9011976A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN121107723A (zh) * 2025-11-14 2025-12-12 矿冶科技集团有限公司 一种胶磷矿浮选尾矿制备镁基胶凝材料的方法及镁基胶凝材料

Also Published As

Publication number Publication date
NZ233232A (en) 1992-09-25
EP0469002A4 (en) 1992-12-02
WO1990011976A1 (en) 1990-10-18
CA2051414A1 (en) 1990-10-06

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