CN1123652C - Technology for preparing Tobemolai stone crystal whisker by water heating of chelate method - Google Patents
Technology for preparing Tobemolai stone crystal whisker by water heating of chelate method Download PDFInfo
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- CN1123652C CN1123652C CN 01132285 CN01132285A CN1123652C CN 1123652 C CN1123652 C CN 1123652C CN 01132285 CN01132285 CN 01132285 CN 01132285 A CN01132285 A CN 01132285A CN 1123652 C CN1123652 C CN 1123652C
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- tobemolai stone
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Abstract
The present invention relates to technology for hydrothermal preparation of Tobemolai stone crystal whiskers by a chelating agent method, which belongs to the field of ceramic crystal whiskers. The present invention is characterized in that Ca(OH)2, amorphous state SiO2 and an ethylenediaminetetraacetic acid (EDTA) are used as raw material, prepared according to a definite proportion and then added into deionized water, and a concentration is between 0.01 mol/L to 0.05 mol/L; Ca<2+>/Si<4+>=1.0-2.0, and the pH value of a solution which is between 13 and 14 is regulated by NaOH or KOH; subsequently, the solution is placed in a reaction vessel to carry out hydrothermal reaction under the conditions of 180 DEG C to 250 DEG C and 2.0Mpa to 3.0Mpa for 3 to 10 hours; in this way, the Tobemolai stone crystal whiskers with a diameter of 0.1 to 1 mu m and a length of 40 to 100 mu m are generated. The present invention has the advantages of simple technology and low cost; all the products are the Tobemolai stone crystal whiskers and do not contain foreign matter; the Tobemolai stone crystal whiskers can be stabilized to be 1150 DEG C, so the Tobemolai stone crystal whiskers can meet the use requirements of fields of thermal-insulating and ultra-light building material and artificial wood, etc.
Description
Technical field
The present invention relates to the preparation of Tobemolai stone crystal whisker, belong to the ceramic whisker field, be mainly used in fields such as thermal insulation, fire-resistant, ultralight building materials and imitation wood.
Background technology
In the calcium silicate hydrate whisker, using at present mainly is xonotlite (Ca
6Si
6O
17(OH)
2) and Tobemolai stone (Ca
5Si
6O
16(OH)
24 (H
2O)) whisker.In production in the past and the experiment, the Tobemolai stone crystal whisker generally all is to carry out hydro-thermal reaction by the suspension to silicon-dioxide and calcium hydroxide at about 200 ℃ to make.Yet, in temperature-rise period, along with the rising of temperature exists CSH intermediate product and intermediate reactions such as (calcium silicate hydrates of low-crystallinity); And the crystallization shape of final product (as: diameter, length, length-to-diameter ratio) also is subjected to the influence of factors such as initial feed crystal form, granular size and distribution, water-solid ratio, thereby large-sized Tobemolai stone crystal whisker is difficult to obtain.
People such as Kunugida point out, do not experience the CSH intermediate product, and the calcium silicate hydrate whisker is directly generated, and the fibrous calcium silicate hydrate whisker of this involutory growth is vital.This understanding has obtained should demonstrate,proving of experiment: Kunugida etc. and has reacted 5 hours for interior 350 ℃ at continuous high pressure still (continuous-type autoclave) by the instant batch mixing (in situ mixing) and the technology that is rapidly heated, and obtaining overall dimension is the xonotlite whisker of 2mm; People such as Yanagisawa reacted 72 hours for interior 250 ℃ at many cavity types autoclave (multichamber-type autoclave) by the method for ion diffusion, obtained to be longer than the xonotlite whisker of 100 μ m.Yet,, need special equipment or higher temperature and long reaction times though more than experiment has been synthesized than big scale xonotlite whisker.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of large-size Tobemolai stone crystal whisker, this method need not special equipment, and Preparation of Whiskers only needs lesser temps and short period.
Technical scheme of the present invention is as follows: with Ca (OH)
2, white carbon black (non-crystalline state SiO
2), ethylenediamine tetraacetic acid (EDTA) (EDTA) is raw material, with KOH or NaOH regulator solution pH value, preparation contains Ca
2+, SiO
3 2+And Ca
2+The solution of chela and thing, wherein Ca
2+Concentration between the 0.01-0.05 mol, Ca
2+/ Si
4+=1.0-2.0, pH value of solution value 13-14; Obtain solution is placed reactor, at 180 ℃-250 ℃, 2.0-3.0Mpa, carry out hydro-thermal reaction under the 3-10 hour condition, generation diameter, length are respectively the Tobemolai stone crystal whisker of 0.1-1 μ m, 40-100 μ m.Treat still cooling, suction strainer solution, repeatedly wash reaction product with deionized water, dehydrated alcohol after, reaction product is placed in the baking oven, dry through 12 hours in 80-120 ℃.
Prepare in the Tobemolai stone crystal whisker process at chelate method, because calcium ion Ca
2+Release mainly at hot stage, this moment is in the equilibrium temperature scope of Tobemolai stone, thus when solution reaches supersaturation for Tobemolai stone the time, formation Tobemolai stone nucleus in the solution.(for example, nucleus CSH) is unstable in this temperature range, and dissolving disappears rapidly for other phase of the minority of Xing Chenging before this.Moreover, calcium ion Ca
2+The speed that is discharged in the solution is slower, so the nucleation process of Tobemolai stone does not have " burst " like that in the hydro-thermal reaction of no sequestrant, forms a large amount of nucleus in very short moment, and is difficult to obtain the big scale whisker.Thereby in whole process of preparation, Tobemolai stone nucleation process is more concentrated, and most Tobemolai stone crystal whiskers directly generate, and without intermediate reaction; And controlled the one-tenth nuclear volume, thereby prepared the Tobemolai stone crystal whisker of big scale.
The Tobemolai stone crystal whisker of method preparation provided by the invention is in 3-10 hour hydrothermal treatment consists of 180-250 ℃ of insulation, and its X-ray diffracting spectrum shows that hydro-thermal reaction is complete, has not had the CSH phase in the product; The halfwidth of each diffraction peak is all narrower, this explanation gained Tobemolai stone crystal whisker complete crystallization; And, (001) and (h01) crystal plane direction diffracted intensity height, and (0k0) the crystal plane direction diffracted intensity is low, illustrates that whisker prolongs growth (Fig. 1) along the b direction of principal axis.
By the sem analysis of Fig. 2, the Tobemolai stone crystal whisker length that records the chelate method hydrothermal preparation is 40-100 μ m, the about 0.1-1 μ of diameter m; The crystallization shape of whisker is typical macrofiber shape; Whisker dispersed fine; And the whisker size dimension is more even.This be because nucleation process more concentrated, major limitation within 180 ℃ of-250 ℃ of temperature ranges, the result of whisker synchronous growth.
By Fig. 3 analysis as can be known, the Tobemolai stone crystal whisker of chelate method hydrothermal preparation still can keep its pattern (this moment, whisker changed β-wollastonite phase into) substantially 1150 ℃ of following thermal treatments after 2 hours; Up to 1200 ℃ of following thermal treatments after 2 hours, just progressively fusion bonding of whisker (whisker changes into d-wollastonite phase).As seen, the Tobemolai stone crystal whisker of chelate method hydrothermal preparation has thermostability preferably.
Ca in solution
2+, Si
4+Concentration, Ca
2+/ Si
4+Ratio is all constant, and the pH value drops at 12.0 o'clock by 13.0, although the hydrothermal treatment consists time also prolongs (becoming 10 hours by 5 hours) accordingly, the pattern of reaction product is completely different, becomes the circle sheet shape by typical minute hand shape.This proves in the method provided by the invention, and pH=13.0 is really and necessary (Fig. 4 sees embodiment 2 for details).
Chelate method hydrothermal preparation Tobemolai stone, technology is simple, and cost is low; The Tobemolai stone crystal whisker structural integrity of preparation, good dispersity; Product all is the Tobemolai stone crystal whisker, does not contain other foreign material (as CSH phase or Tobemolai stone crystal grain etc.); And can be still very stable until 1150 ℃, just bond after 1200 ℃ (changing α-wollastonite phase into), this illustrates that method provided by the invention can control preferably to Tobemolai stone crystal whisker pattern, and the Tobemolai stone crystal whisker Heat stability is good of producing, can satisfy the service requirements in fields such as adiabatic, fire-resistant, ultralight building materials and imitation wood.
Description of drawings
The different hydrothermal treatment consists time gained Tobemolai stone crystal whisker X-ray diffracting spectrums of Fig. 1: (1), (2), (3) are represented respectively under 200 ℃ of temperature, 3,5,10 hours hydrothermal treatment consists product X-ray diffraction collection of illustrative plates.
The different hydrothermal treatment consists time gained Tobemolai stone crystal whisker SEM patterns of Fig. 2: (A), (B), (C) represent under 200 ℃ of temperature 1,3,5 hour hydrothermal treatment consists product respectively.
The SEM pattern of thermal treatment Tobemolai stone crystal whisker after 2 hours under Fig. 3 differing temps: (A) 800 ℃; (B) 900 ℃; (C) 1000 ℃; (D) 1100 ℃; (E) 1150 ℃; (F) 1200 ℃
Fig. 4 pH value equals 12.0 o'clock hydrothermal treatment consists reaction in 10 hours gained Tobemolai stone SEM pattern.
Embodiment
The invention will be further described below in conjunction with example, but only be confined to embodiment by no means.
Embodiment 1 operation steps is as follows
(1) with 23.38 gram ethylenediamine tetraacetic acid (EDTA)s, 6.055 gram Ca (OH)
2, 2.402 gram white carbon black (non-crystalline state SiO
2) add in 2 liters of deionized waters, with KOH regulator solution pH value to 13.0, stir until clarification;
(2) will be equipped with solution and pour in the reactor, 200 ℃ are incubated 5 hours down;
(3) treat the still cooling, suction strainer solution repeatedly washes the Tobemolai stone crystal whisker that reacts gained with deionized water, dehydrated alcohol;
(4) the Tobemolai stone crystal whisker is placed in the baking oven 80 ℃ of oven dry in following 12 hours.
Mutually shown in (2) among Fig. 1, the SEM morphology analysis and shows good thermostability shown in Fig. 2 (c), still keeping its pattern (Fig. 3 (E)) in 2 hours substantially through 1150 ℃ of thermal treatments by the thing of the Tobemolai stone crystal whisker of present embodiment growth.
Embodiment 2 operation stepss are as follows
(1) with 23.38 gram ethylenediamine tetraacetic acid (EDTA)s, 6.055 gram Ca (OH)
2, 2.402 gram white carbon black (non-crystalline state SiO
2) add in 2 liters of deionized waters, with KOH regulator solution pH value to 12.0, stir until clarification;
(2) will be equipped with solution and pour in the reactor, 200 ℃ are incubated 10 hours down;
(3) treat the still cooling, suction strainer solution repeatedly washes reaction product with deionized water, dehydrated alcohol;
(4) reaction product is placed in the baking oven 80 ℃ of oven dry in following 12 hours.
Though other conditions of present embodiment are with embodiment 1, only pH value is 12.0, although soaking time prolongs 1 times, but still can not obtain satisfied whisker, so pH value 13-14 is necessary.
Claims (4)
1. the Technology of a chelate method hydrothermal preparation Tobemolai stone crystal whisker is characterized in that:
(1) with Ca (OH)
2, non-crystalline state SiO
2, ethylenediamine tetraacetic acid (EDTA) is raw material, joins in the deionized water, regulates the pH value to 13-14 with alkali metal hydroxide, be mixed with to contain Ca
2+, SiO
3 2+And Ca
2+The solution of chela and thing;
(2) above-mentioned solution is placed reactor, at 180 ℃-250 ℃, synthetic under the 2-3MPa condition through 3-10 hour hydro-thermal reaction;
(3) treat the still cooling, suction strainer solution repeatedly washes reactant with deionized water, dehydrated alcohol, 80 ℃ of-120 ℃ of oven dry.
2. by the Technology of the described chelate method hydrothermal preparation of claim 1 Tobemolai stone crystal whisker, it is characterized in that being mixed with and contain Ca
2+, SiO
3 2+And Ca
2+Ca in the solution of inner complex
2+Concentration between the 0.01-0.05 mol, Ca
2+/ Si
4+=1.0-2.0.
3. by the Technology of the described chelate method hydrothermal preparation of claim 1 Tobemolai stone crystal whisker, it is characterized in that described alkali metal hydroxide is NaOH or KOH.
4. by the Technology of the described chelate method hydrothermal preparation of claim 1 Tobemolai stone crystal whisker, it is characterized in that described drying time is 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01132285 CN1123652C (en) | 2001-11-23 | 2001-11-23 | Technology for preparing Tobemolai stone crystal whisker by water heating of chelate method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01132285 CN1123652C (en) | 2001-11-23 | 2001-11-23 | Technology for preparing Tobemolai stone crystal whisker by water heating of chelate method |
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|---|---|
| CN1358885A CN1358885A (en) | 2002-07-17 |
| CN1123652C true CN1123652C (en) | 2003-10-08 |
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|---|---|---|---|
| CN 01132285 Expired - Fee Related CN1123652C (en) | 2001-11-23 | 2001-11-23 | Technology for preparing Tobemolai stone crystal whisker by water heating of chelate method |
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| SI3247684T1 (en) * | 2015-01-19 | 2021-10-29 | Cimpor Portugal Sgps Sa | Methods for manufacturing amorphous low-calcium content silicate hydraulic binders |
| CN104911715A (en) * | 2015-07-02 | 2015-09-16 | 瓮福（集团）有限责任公司 | Method for preparing calcium silicate crystal whisker from fluorine-contained silicon slag |
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Granted publication date: 20031008 Termination date: 20131123 |