CN86101506A

CN86101506A - The growth method of colour crystal

Info

Publication number: CN86101506A
Application number: CN86101506.1A
Authority: CN
Inventors: 仲维卓; 华素坤
Original assignee: Shanghai Institute of Ceramics of CAS
Current assignee: Shanghai Institute of Ceramics of CAS
Priority date: 1986-06-27
Filing date: 1986-06-27
Publication date: 1988-01-06
Also published as: CN1003459B

Abstract

The growth method of colour crystal of the present invention, (solvent of NaOH-KOH) has been chosen favourable seed crystal cut type (+Y ,-Y, (30-80 degree) X cut) according to the crystal structure habit, adds suitable dopant ion (Al to adopt mixed base ³⁺, CO ²⁺, Fe ³⁺, Fe ²⁺, Mn ⁴⁺).Under 1200-1600 normal atmosphere, growth temperature is 335-360 ℃ in autoclave.The temperature difference is 15-25 ℃, and it is even to grow quality, and the productive rate height does not have cottonly, and no twin crystal, crackle and bubble etc. are suitable for the high-quality color crystal of practicality.

Description

Involved in the present invention is growing method, particularly utilize in the NaOH-KOH mixed solvent, employing+Y ,-seed crystal of Y, (the 30-80 degree is cut) and X cut type is with " the terraced method of hydro-thermal temperature " the grow method of citrite (smoky quartz).

Citrite is a kind of of colour crystal, and it is a kind of ideal material of making the yellow quartz mirror; Also can be used for many new technical field, the protection of the incandescence that sends in protection, other technical field such as the smelting iron and steel as the incandescence that rocket, guided missile sent.China northeast and northwest drought and desert region need a large amount of citrite glasses, (estimate annual about 30-50 ton.）

In the past, citrite was that mineral crystal makes behind gamma-ray irradiation.Because mineral crystal extremely lacks, supply falls short of demand; In addition, the mineral crystal defective is many, and cotton, inclusion, twin crystal, crackle etc. are arranged, and quality is inhomogeneous behind the irradiation, so need carry out synthetic.

The method of existing synthetic citrite can be divided into two kinds substantially:

First kind: during growing crystal, be to adopt in yellow soda ash (or salt of wormwood) solvent, to add dopant ion (FeCO ₃, MnCO ₃, CoCO ₃) formation ion look.(" crystallization engineering " Ha Application De Block ッ Network p.984,1971; The synthetic of colour crystal " piezoquartz technology " 1984.4; " artificial lens " 1985.Vol14 № 2）。But in above-mentioned solvent, the crystal of being grown, quality is inhomogeneous, and the also difficult control of color.Its growth technique is also stable inadequately, and there is the crack in the growth later stage, and crystalline state is bad, and it is slow to grow up, poor repeatability.

Second kind: be in single NaOH solvent, to add Al ³⁺, the crystal of being grown shows dark brown behind gamma-ray irradiation.(Kristallografiya Vol.12 № 1 65-9(1967) Phys, stat.Sol.(a) 29,659(1975)), this is studied mainly from Al ³⁺Colour center effect in crystal is set out, and inquires into the formation of dark brown crystalline substance (smoky quartz), has at length studied crystalline spectral line of absorption and Al ³⁺The mechanism that colour center forms.But cut type and quality homogeneity to the speed in the crystal growth, seed crystal there is no report.

Common a kind of cranberry glass on the market, its hardness low (Mohs' hardness is 5), not anti-windsand mill corrosion is made dark brown glasses, and the smooth finish life-span is long not as good as quartzy.

Purpose of the present invention is to provide a kind of citrite that is used to make dark brown glasses (smoky quartz) growth method of market in urgent need.The feature of this method is: 1. adopt NaOH-KOH mixed base solvent.2. seed crystal need edge+Y ,-the Y(30-80 degree) and the X cut type make crystal growth rate fast, quality is even, the crystal growth size is easy to control, cost is low.

Technology contents of the present invention is as follows:

One, the pre-treatment of raw material:

Adopt 3-4 level smelting quartz and vein quartz, wash, And uses salt acid soak 24 hours, cleans, dries with distilled water again.Stand-by.

Two, the preparation of growth solution:

Adopt NaOH(1-1.5N), KOH(0.3-0.8N) be made into mixed solvent, add main dopant ion Al ³⁺(weight %, as follows) 0.1-0.5%; Also can be according to the needs of color, select to add different ions: blueness adds Co ²⁺0.1-0.5%; Lemon yellow Fe ²⁺0.1-0.3%; Purple adds Fe ³⁺(solvent NaCl) 0.1-0.5%; Blackish green Mn ⁴⁺0.1-0.6%.

Three, seed crystal cut type and pre-treatment:

Cut type+Y 30-80 degree

-Y 30-80 degree

X cuts

Seed crystal thickness is 2 millimeters.With ultrasonic drilling (or drill bit punching).

Seed crystal is washed, put into washing lotion again and soaked 24 hours, wash, stand-by.

Seed crystal after cleaning is worn with iron wire and to be tied on the seed crystal frame.

Four, crystalline growth:

It is to have the seed crystal frame of seed crystal to pack in the still that the stand-by quartz raw material of oven dry is packed in the vertical autoclave.Pour the height that the mixed base solvent ， And for preparing measures liquid level in the still into, compactedness is the relative still volume of 80-83%().Autoclave packed into heat, heat in the holding furnace.

Growth temperature is controlled at 335-365 ℃

Temperature difference 15-25 ℃

Pressure 1200-1600 normal atmosphere

Growth velocity 0.6-1.3 millimeter/sky

Five, crystalline irradiation:

Behind the growth ending, take out crystal Co ⁶⁰Irradiation, dosage is: 1 * 10 ⁵-10 ⁷Rad.

Effect of the present invention is: owing to adopted preferential orientation and mixed base (NaOH-KOH) solvent that meets Growth Habit, make crystal growth rate improve 30-40%; Owing to controlled adulterated distribution, through Co ⁶⁰Irradiation, gained crystal quality is even, and reaching does not have cotton, and no twin crystal, crackle and bubble etc. meet the requirement of making the yellow quartz mirror fully.

Below with tabular form effect of the present invention is described:

Table one, seed orientation and growth velocity, the inhomogeneity relation of quality

Table two, Al ³⁺Doping is to the influence of crystal growth rate and quality (cut type Z, X)

The comparison of table three, citrite and cranberry glass

Citrite is durable in use and graceful luxurious, more is applicable to make dark brown glasses.

Performance of the present invention describes by table four.

Table four has been listed the growth performance of citrite, and the effect that is reached under each condition.

Table five has been listed adulterated ionic species of colour crystal and concentration range performance.

Table five, colour crystal dopant ion and concentration range thereof

Claims

1, a kind of employing NaOH makes solvent, with Al ³⁺(Co ²⁺, Fe ³⁺) ion is as the growth method of the synthetic colour crystal of doping agent, it is characterized in that:

A. adopt NaOH-KOH mixed base solvent;

B. seed crystal need edge+Y ,-Y, X cut type;

C. need to select dopant ion and concentration range thereof;

D. crystal need carry out Co ⁶⁰Irradiation.

2, growth method according to claim 1 is characterized in that:

The concentration of mixed base solvent is

NaOH 1-1.5N， KOH 0.3-0.8N。

3, growth method according to claim 1 is characterized in that:

The seed crystal cut type is+the Y30-80 degree

-Y30-80 degree

X cuts.

4, method according to claim 1 is characterized in that:

Co ⁶⁰Irradiation dose be: 1 * 10 ⁵～10 ⁷Rad.

5, growth method according to claim 1 is characterized in that:

Selectable dopant ion, and concentration range is:

Dark brown Al ³⁺0.1-0.5 weight %(is as follows)

Purple Fe ³⁺(solvent Nacl)

Blue look Co ²⁺

Lemon yellow Fe ²⁺(add K ₂CO ₃)

Blackish green Mn ⁴⁺(add K ₂CO ₃).

6, growth method according to claim 1 or 5 is characterized in that:

Growth temperature is controlled at 335-365 ℃

Temperature difference 15-25 ℃

Pressure 1200-1600 normal atmosphere.