JPS60246218A - Restrictedly swelling synthetic mica and its preparation - Google Patents

Abstract

PURPOSE:A novel restrictedly swelling type synthetic mica in which the amount of Li as an octahedral layer ion in conventional synthetic mica is reduced, instead, Mg is increased and the chemical constitution is specified, thus giving platelets of small average sizes by easy cleavage. CONSTITUTION:The objective synthetic mica has a chemical constitution of the general formula (X represents Mg<2+> or a mixture thereof with Fe<2+>, Ni<2+>, Mn<2+>, Al<3+> or Fe<3+>, Y represents Si<4+> or a mixture thereof with Al<3+>, Fe<3+> or B<3+>, and x is 0 or 0.5<x<0.9), or typically NaMg2.5-x/2LixSiO10F2 (II). The objective mica is prepared by using starting materials in chemically stoichiometric amounts, except for F, which is used in an excessive amount. The composition is melted by heating through a known process such as stay melting or flame melting, preferably at about 1,000-1,500 deg.C, then cooled down. In this process, Zr, or B compound can be added as a seed for fine-particle crystallization.

Description

[Detailed description of the invention]

(Industrial Field of Application) The present invention relates to a limited swelling type synthetic mica and a method for producing the same, and more specifically, the present invention relates to a limited swelling type synthetic mica and a method for producing the same.
This invention relates to a limited swelling type synthesis which produces scale-shaped particles Jf with a small diameter, and an advantageous method for producing the same. (Conventional technology) Conventional natural cloud fit, fu, and sounba I do not have IV resistance even when soaked in water.
1/Synthesis of a species that does not hydrate but has certain conditions 7 Miha 1 has 1 hydration swelling + 1'', that is, the ability to pull water molecules between the crystal layers and rise up + 1. This hydration-swellable mica has a "limited swelling cloud" ij 44 in which only a limited layer of water molecules coordinates, and a free water-like tendency.
It is divided into two types: 1st mica, which takes in water, and 1st mica, which takes in water. The present invention relates to a limited Dojun type cloud rrl,
Conventionally, such a synthetic JJ is 1 public 11/l 3
5-8874, the type tetrasilicon cloud r+J was known. (The problem that the invention seeks to solve)

[-21,) However, the fruit C7+, t, described in the specification, has a force that tightens the interlayers, so-called interlayer strength, so it can easily be folded, and has a small uniform grain size. I can't get J1.'! It is therefore an object of the present invention to provide a novel limited swelling type composite i, +51ij which can be easily folded to remove scales with a small average grain size, and a method for producing the same. The limited swelling pear cloud f + J crystal structure i shield is! The octahedral layer consists of a kefiic acid tetrahedral layer of −・g and ions forming an octahedral layer which is inoculated with the tetrahedral layer, and the octahedral layer consists of four M elementary ions and two It is composed of six anions consisting of six fluorine ions, and Mg and I-i coordinated at the center of the anion. In the ion configuration inside this five-layer lattice, +
``The charge balance between '@meren and negative electric Kusunoki is such that there is a lack of +1 electric 6X ■, so to compensate for this shortage, r interlayer ions are placed between the -1 layer r and S layer f] The inventors focused on this principle of charge balance, and by varying the amount of Ll, which is a positive ion in the octahedral layer, the interlayer strength was improved. I thought it might be possible to change the
The present invention was arrived at after many series of experiments. (Means for Solving the Problems) That is, the present invention provides general formula 1: % formula % () (wherein X is Mg2+ or Mg2+ as well as Fe",
Contains +, Mn, AI"+ or Fe"+2+ 2
+ represents the 114 compound ion, Y is S14+ or S4
ljt containing AI, Fe or B along with + 3+ 3+ 3 + 1
represents a compound ion, and X is selected from the range of 0.5 x<0.9. ), we present a limited tll-type synthetic cloud I with a chemical composition of 4r, and we also have fluorine source, silicon source, magonuno, source, sodium source, source,
A lithium source and an oxygen source, 2+0, are blended, and if desired, Fe, Ni"1, Mn
, AI, Fe3+, and S3+ A mixture containing one or more 2+ 3+ ion sources is heated and melted, and then cooled to form the general formula I
5 PB expressed as >if swelling type synthesis ′j: liJ
The present invention provides a method for manufacturing. First, the lithium ion in the synthetic mica of the present invention has an index X of 0.5<x<0.9, preferably 0.6<x<0.
．． 8, and when X≦0.5, the self tll 1IiiiJ runse 1 is made small, and it does not become a limited swelling type cloud +a, and when X≧09, the conventional synthesis Cloud nl NaMg 2LiS l, Olo F 2
The M1 configuration approximates that, and its +”l ff!t is also 11
It is a synthetic mica that resembles , has high interlayer strength and is difficult to peel off. The relationship is that while Li is X, Mg is 2°5-x/
It needs to be 2. This is because in the present invention, since the wrinkles of Ll are reduced, a lack of charge occurs in the octahedral layer, but this lack of charge is compensated for by increasing the amount of Mg. In any case,
If this inoculation relationship is not formed into a swirl layer, the synthetic cloud fkj that is the object of the present invention cannot be obtained. A typical example of the invention is represented by the following formula II: N a M g2. s-! /2L IS! i, 0
1oF 2(■I)! (In the formula, X represents the above meaning.) and,! , Mg ions in the octahedral layer of formula II are partially replaced by F2+, 2+ due to the known isomorphic substitution relationship.
Substitution with 2+ 3+ e , Nl 2 , Mn 2 , AI or 30Fe 2 can yield micas of similar properties encompassed by formula I above. The amount that can be replaced is M
It is within about 20% of g. Also, Sl in the tetrahedral layer has the same isomorphic substitution relationship of 3+3+, so A1. Substitute with Fe or B3+. It is also possible to obtain a cloud f+J with similar properties included in the above formula (2). About 1 of Si can be substituted
It is within 0%. Of course, there is no increase or decrease in charge before and after these isomorphic substitutions. The production of the composite mica represented by the general formula I used in the present invention is carried out using chemical ratios of each raw material to the desired product, or ratios in which only fluorine is contained in a ratio greater than this ratio. The mixture may be blended so that it becomes, heat-melted, and then cooled. Here, the original 47-2 element is easily volatilized, and therefore, when heated with a normal device, it will volatilize to some extent, so it is preferable to mix it in an amount corresponding to that amount. Raw materials fluorine source, silicon source, magnesilla 1. i. Sodium source, lithium source and oxygen source may constitute the chemical composition of the product as a single substance or a combination of compounds;
Alternatively, any material may be used as long as a part of the composition of the raw material is volatilized during production and forms the chemical composition of the product, such as -1 silicon oxide, magnesium oxide, magnesium fluoride, etc. , magnesium chloride
1. fluoride)・lium, trifluorosilicate 11. Sodium carbonate, sodium fluoride, lithium carbonate, and the like are preferably used. In addition, as an ion source for isomorphic substitution of S, for example, iron oxide (Fed) and iron oxide (FeF2) are used for Fe2+, N
1, for example, nickel oxide (Nip) and nickel fluoride (NiF2), and Mn, for example, manganese oxide (MnO) and manganese fluoride (MnF2).
), but A; is, for example, aluminum oxide (A I 2
03) and aluminum fluoride (AlF2) is Fe3
For example, iron oxide (Fe203) and iron fluoride (F
e F 3) is 3+, B is, for example, sodium borofluoride (NaBFa)
is preferably used. Heat melting is preferably carried out by a known method such as a band melting method, a flame melting method, an internal combustion electric melting method, etc. to a temperature of about 100°C to 15°C.
This can be carried out by heating to 00'c. Cooling may be performed, for example, by a known mold cooling method or ventilation cooling method. At that time, the cooling rate is 1°C/min to 3°C/min.
It is difficult to carry out the cooling at 0°C/min, and if the cooling rate is too slow, it will not be possible to obtain a small cloud with an average particle size of 1
On the other hand, if the cooling rate is too high, do not crystallize.
It becomes crow-like. On the other hand, the conventionally known limited we type snow cloud U
]・Liumtenioli L (NaMg2LiSi40
．． In o), raw polymer compounds are blended to have a stoichiometric composition, heated and melted, and then heated at 5°C/l.
VII by slow cooling at an in-circle cooling rate between If
However, in the method of the present invention, the cooling conditions are changed to W. In the production method υ of the present invention, a zirconium or holon compound can be blended as a crystal Wi granulating agent. In order to expect the added effect of the collar, the amount of zirconium 4-sig should be approximately O11 to poron equivalent for the entire composition.
It is preferable to mix 0.311'+v%. (Example) Next, the present invention will be further explained with reference to Examples of the present invention, but the present invention is not limited to these Examples. Example 1 The following formula: 34 Na, , SiF6.24Mg0.3/]OLi
100 kg of a formulation having the following mold composition corresponding to the stoichiometric ratio expressed as 2CO3-3'A 5in2 was prepared. Sodium silicide (Ha S+F e ) 22
．． 7% Magnesium oxide (MgO) 21.4% Lithium carbonate (Li2 C03) 5.3 Oni Shi'l :b (
S102) 50.8% The blend described in 1- above was charged into an internally heated electric melting furnace, and heated by applying electricity to melt the blend. The melt temperature of the melt was 1350'C. After melting is complete, pour the melt into a steel mold and heat at 16°C/
It was cooled at a cooling rate of 1 minute. The cooling rate is a temperature effect/elapsed time value, which was determined by continuously measuring the temperature with the P-R heat couple. The obtained crystal mass was immersed in water, thoroughly washed with distilled water, and the sample was chemically analyzed.The chemical Al1 composition of this cloud was determined by the following formula: NaMg2.2! -1o, B S+40 10F 2
It was recognized that fk is expressed by (Formula II, x=0.6i). Furthermore, the low-planar spacing during unshielding was 12.6 A, which revealed that this crystal was of a limited swelling type. Example 2 100 kg of a formulation with a weight composition corresponding to the stoichiometric proportions expressed by the following formula: % formula % was prepared. Sodium silicofluoride (Na 2 S + Fe) 2
2-5% Magnesium oxide (MgO) 20.2%
Lithium carbonate (L12 C03)? , IX silica (
Si02) 50.2% Using this blend, a crystal mass was obtained by a method similar to Example 1111. Example 3 2 A crystal mass was obtained in the same manner as in Example 2, except that the cooling rate was 4°C/min. Example 4 The formulation of Example 2 was further supplemented with sodium borofluoride (Na
A crystal mass was obtained in the same manner as in Example 2 except that BF4) 5 Kg was added. Example 5 A crystal mass was obtained in the same manner as in Example 2, except that 25 K g of sodium zirconium fluoride (NaZrFs) 1 was further added to the formulation of Example 2. Comparative Examples 1 and 2 Crystal lumps were obtained in the same manner as in Example 3, except that the cooling rate was set to 0.1°C/min (Comparative Example 1) or 50°C/min (Comparative Example 2), respectively. Comparative Example 3 Blend 1 with the following weight composition corresponding to the stoichiometric proportions expressed by the following formula: % Formula %. OOK g was prepared. Tritrium (Na2)
S+F e ) 2L 2% magnesium oxide (Mg
O) 24.9X Silica (S+02) 5], 9% Force 7 min as in Example 1 using this formulation. A crystal mass was obtained. Comparative Example 4 100 kg of a blend with a weight composition corresponding to the stoichiometric ratio expressed by the following formula: % was prepared. Sodium silicofluoride (Na 2 SiF 6) 22
．． 8X Magnesium Oxide (MgO) 22.5% Lithium Carbonate (Li2C03) 3.6X Silica (S+02
) 51.1 pieces Using this blend, a crystal mass was obtained using the same force 1) as in Example 1. Comparative Example 5 A formulation with the following weight composition corresponding to the stoichiometric proportions expressed by the following formula: 1. OOK g was prepared. Sodium silicide 1, (Na 2 SiF 6) 2
2.3% Magnesium oxide 1, (MgO) 19.1%j
R%') f Ut, (Li2C03) 8.8$ Silica (Sin, ) 49.8χ Using this blend, a crystal mass was obtained in the same manner as in Example 1. Next, measurement of average particle diameter and test examples of delamination and swelling properties of the products obtained in Examples 1 to 4 and Comparative Examples 1 to 5 will be shown. Each test was conducted as follows. (Layer Peeling Test) Synthetic cloud hl l OOg is put into 200 mQ of 3% n-butylamine hydrochloric acid solution and reacted. Next, the obtained reaction product is washed and swollen with distilled water. The mica complex thus obtained is separated from the unfolded mica by passing it through a 100 mm sieve. The ease of delamination is evaluated based on the amount of unfolded mica. Those in which the amount on the sieve 1- of the loo mensch was 30% of the total weight were designated as V-defective and 1, and those less than 30% were designated as r-1. (Measurement of average particle size) The sieve vine obtained in the above test was
Centrifuged for 0 minutes. The 1st part of the solution was measured using a light transmission type particle size distribution analyzer, and the 4% average particle size was determined as 50% of the average particle size. (Swelling Test) Synthetic mica powder was ground in a mortar and placed on a Holter, water was added to it using a dropper, and the swelling l1flM was determined based on the X-ray diffraction peak in the wet state. (OO1
) From the diffraction W, if a clear peak appears around 2θ = 56″ to 8.8°, it is defined as 1 limited swelling property j, and 20 = 9″
A case where the baseline of I.A was gentle and no clear peak appeared at 2θ=2° to 9″ was defined as 1 “free swelling property”. Next, the test results described in ■- are shown in the following table. 6 (Effect) It is thought that by decreasing Li, which is an octahedral layer ion of conventional synthetic clouds, and increasing Mgl by that amount, the interlayer strength became weaker, and as a result, the following The effect is irritating. (Effects of the Invention) From the above test results, the limited swelling synthetic mica of the present invention has particles that are easier to delaminate and have a smaller average particle size than the conventional limited swelling synthetic cloud Iυ. I understand that. Patent applicant Dobby Ohgyo Co., Ltd. Attorney Hitoshi Inagaki 8

Claims (1)

[Claims] (1) General formula ■・NaX2.5-1/2 X 4 10 2LiY OF
(1) (In the formula, X is Fe”2 along with M S2+ or Mg2+
represents a mixed ion containing + 2+ 3+ , N+ , Mn , AI or Fe3+, and Y is S14+ or S4+ 3+
3+ 3 + 1 represents a mixed ion containing AI, Fe or B, and X is selected from the range of 0.5 x<0.9. ) A limited swelling synthetic mica characterized by having a chemical composition represented by: (2) General formula ■I: Na Mg2.5-. 72Li, S i 40. oF
2(II) (wherein, X is selected from the range of 0.5<x<0.9). 3) Finger x
The synthetic mica according to claim 1 (i) or 2 (i), wherein is selected from the range of 0, 6<x<0, 8(7). (4) Combining a fluorine source, a silicon source, a magnesilane source, a sodium source, a lithium source, and an oxygen source, and optionally further Fe, N+, Mn, and AI.
The general formula 1% formula % (1) is characterized by heating and melting a compound containing a type of iono2 + 3+ 3+ source consisting of , Fe 2 and S3+, and then cooling. Fe”2+ with Mg2+ or Mg2+
2+ 3+ , N+ , Mn , AI or Fe”+, Y represents S14+ or S4+ 3+
3+ 3 + 1 together with A1. represents a mixed ion containing Fe or B, and X is selected from the range 05 x<0.9. ) The production of a liminal swelling type synthetic cloud having the chemical composition shown in Table 1. (5) Claim No. 4111 in which Nrukoniu 1, Compound 1 compound, or a boron compound is blended as a crystal atomizing agent.
Synthetic cloud f (j's V-creation force).