CN1461825A - Nickel iron sulphate dodecahydrate crystal used for ultraviolet and blue-green light-flux belt filter - Google Patents

Abstract

A FeNi(SO4)2.12H2O crystal used for ultraviolet and blue-green light flux bolt filter is disclosed. It is grown in a growing solution at ordinary temp-65 deg.c for 0.5-1 month by using sulfuric acid to regulate its pH value to 1.5-2.5 and rotating it at 30-60 rpm.

Description

The ten sulfate dihydrate ferronickel crystal that are used for ultraviolet and blue green color passband wave filter

Be used for ten sulfate dihydrate ferronickel crystal of ultraviolet and blue green color passband wave filter, relate to optics and artificial crystal material.

The ten sulfate dihydrate ferronickel crystal that are used for ultraviolet and blue green color passband wave filter use the monocrystalline pass filter can make special spectral wavelength by getting rid of other wavelength.Must have the feature that is discontinuity through spectrum as crystal filter, the optical band of passing through be had very high see through efficient and narrow bandwidth and other optical band intensive absorbs.Childy report in 1961 nickel sulfate hexahydrate Ni (SO ₄) 6H ₂O crystal (being called for short NSH) is made the ultraviolet bandpass filter, has been widely used in the wave filter and the transmitter of commercial spectrum, laser technology.We have declared the Chinese invention patent (application number 99108240.0) of " growth method of cylindrical alpha-nickel sulfate hexahydrate crystal " in 1999.The problem of NSH crystal in application mainly is the easy cleavage of crystal, makes to be difficult to obtain being processed into the desired optical surface of device.Its thermostability lower (70 ℃ will be dewatered) makes it to be applied to the higher envrionment temperature in space (～80 ℃) in addition.People such as the Narsingh B. of u.s.a. military affairs industrial (Northnop Grumman Corporation) in 1998 obtain patent of invention (the Narsingh et al. of ultraviolet filter, United StatesPatent, Crystal for Ultraviolet Light Filter, 5,788,765, Aug, 4,1998).Invent a kind of novel ultraviolet filter crystal material-nickel sulfate hexahydrate potassium K ₂Ni (SO ₄) ₂6H ₂O (being called for short KNSH), it has the see through spectrum property similar to NSH, and its thermostability is better than the NSH crystal.Grow the crystal of 2 cm diameters, planned this crystal and make ultraviolet light transducer and be applied to missile early warning system, but difficultly given the crystal that growth obtains the high optical quality of large size.Calendar year 2001, we designed a kind of new ultraviolet filter crystalline material---nickel sulfate hexahydrate ammonium (NH ₄) ₂Ni (SO ₄) ₂6H ₂O (being called for short ANSH), it has UV spectrum character similar to the KNSH crystal and higher thermostability (" nickel ammonium sulfate hexahydrate crystal that is used for ultraviolet filter ", Chinese invention patent, application number: 01132614.x).Defective also appears in this crystal growing process easily, and large size, high-quality crystal technique still need further be researched and solved.

According to the analysis and research of molecular composition, crystalline structure and ultraviolet-near infrared spectrum property relationship, we design a kind of new ultraviolet and blue green glow bandpass filter crystalline material again---ten sulfate dihydrate ferronickel FeNi (SO ₄) ₂12H ₂O (being called for short FNSH).This is a kind of new compound complex compound.At home and abroad there is no the report of synthetic, the crystal growth, crystalline structure spectrum and the thermal property that close this compound at present.

Be used for ten sulfate dihydrate ferronickel crystal of ultraviolet and blue green color passband wave filter, the purpose of its invention is: design and develop a kind of new near-ultraviolet light and blue green light band bandpass filtering modulator material.Make this crystalline material have high transmitance and narrow bandwidth, thermostability to be better than the NSH crystal, grow large-size and optical quality easily and be convenient to processed and applied in the wave filter optical element in above-mentioned two optical bands.

The technical scheme that realizes this invention is as follows:

1. the crystalline material chemical formula is FeNi (SO ₄) ₂12H ₂O (ten sulfate dihydrate ferronickels are called for short FNSH).The synthetic method of raw material is 1: 1 Ni (SO with analytically pure mol ratio ₄) 6H ₂O and Fe (SO ₄) 7H ₂O heating for dissolving postcooling in distilled water obtains bottle-green FNSH crystallization.

2.FNSH growing method

(1), the solubleness of FNSH in water: measure the curve that the solubility with temperature of FNSH in water changes with the saturated solution weighting method, simulate the expression formula of solubleness S.The synthetic method of FNSH is with analytically pure Fe (SO ₄) 7H ₂O and Ni (SO ₄) 6H ₂O heats in water and carries out complex reaction and get bottle-green crystalline particle.Record 35-55 ℃ FNSH-H with the saturated solution weighting method ₂The solubleness expression formula of O is:

S (FNSHg/100gH ₂O)=36.857+0.11314 * t+0.00114 * t ²Can find out that from this formula solubleness and solubility temperature coefficient are bigger, be fit to adopt aqueous solution cooling method growth FNSH monocrystalline.

(2), FNSH crystalline growth temperature can be selected from 65 ℃ to room temperature.The positive and negative velocity of rotation of crystal is 30-60 rev/min, and the temperature-controlled precision of growth groove is ± 0.01-0.02 ℃.

(3), the preparation of FNSH saturated solution: the FNSH saturated solution of using according to the solubleness preparation crystal growth of the FNSH that has measured is 1.5-2.5 with the pH of sulfuric acid regulation solution, to prevent Fe (OH) ₂Precipitation produce, solution is through filtering purifying, slowly reduces to temperature of saturation after overheated being higher than temperature of saturation.

(4), the complete small-crystalline that adopts sporadic nucleation in the saturated solution is as seed crystal, according to the solubleness of FNSH and the real-time long-pending control of crystal growing surface crystalline cooling amount, makes the average speed of growth of crystalline reach 2-3mm/ days, 0.5～January of crystal growth cycle.After crystal growth reaches desired certain size, extract out and take out crystal after saturated solution in the growth groove lowers the temperature crystal to be annealed to room temperature naturally.

3.FNSH crystalline structure measure with CAD-4x ray four-circle diffractometer, determine that this crystalline chemical formula is designed synthetic FeNi (SO ₄) ₂12H ₂O belongs to oblique system, and spacer is P2 (1)/c, unit cell parameters a=9.994 (2) , b=7.2444 (14) , c=24.254 (5) , β=98.83 (3) °, V=1735.5 (6) ³, z=4, Dc=2.001gcm ^-3The molecular structure of FNSH and single crystal structure are seen Fig. 1 and Fig. 2.

4.FNSH crystalline sees through spectrum with PE-λ 900 spectrophotometer measurements, be optical direction with FNSH crystal (001), thickness is 7mm, through optical polish, measure wavelength from 190nm to 1800nm through spectrum.Showing from 190nm-1800nm has two to see through the peak, and a peak is in the near ultraviolet region (300nm), and another peak is at blue green Region (500nm).All there are high transmitance and narrow bandwidth in these two peaks, and remaining wavelength shows as the intensive absorption.This spectrographic discontinuity that sees through is similar to NSH and KNSH crystalline and sees through spectral response curve, is suitable as the bandpass filter and the transmitter of near-ultraviolet light and blue green glow.Utilize its blue green glow to see through, the character of near infrared hypersorption can be used for the spectral filter (even harmonic wave passes through, the first-harmonic hypersorption) of important laser window 1064, the selection of 980nm frequency multiplication, also can be used for the wave selector material of light.The ultraviolet crystal is used for the indication device of optical filter and sees Fig. 3.

5.FNSH the crystalline thermostability is better than NSH crystal, measuring its dehydration temperaturre scope with Delta Series TGA7 thermal analyzer is 80.05-256.12 ℃, illustrates that the FNSH crystal is higher than the NSH crystal filter as the working temperature of the bandpass filter of light.

This invention is compared the beneficial effect that is had with background technology: at known crystalline material with ultraviolet filter performance is NSH, KNSH and ANSH, the new crystal FNSH of ultraviolet filtering of the present invention contrast NSH crystal has the higher and crystal of thermostability and does not have divisibility, and easily optics is processed into the advantage of filter element.Contrast KNSH and ANSH crystal, FNSH crystal growth ratio is easier to obtain large-size, and optical quality is advantage preferably, and this has useful effect to the cost that improves growing efficiency and reduction optical filter.

The ten sulfate dihydrate ferronickel crystal that are used for ultraviolet and blue green color passband wave filter, now accompanying drawing is made brief description: Fig. 1 is the molecular structure of FNSH; Fig. 2 is a FNSH crystal unit cell structure iron; Fig. 3 is the block diagram that the ultraviolet crystal is used for optical filter, and wherein (1) is that display screen, (2) are guided missile for ultraviolet crystal, (4) for light harvesting imaging, (5) for detector, (3).

Being used for ten sulfate dihydrate ferronickel crystal of ultraviolet and blue green color passband wave filter, is exemplary embodiments of the present invention below:

1. raw material: use homemade analytically pure Fe (SO ₄) 7H ₂O, Ni (SO ₄) 6H ₂O and the crystallization of second distillation water dissolution postcooling go out bottle-green FeNi (SO ₄) ₂12H ₂O is as the raw material of FNSH single crystal growing.

2. the preparation of growth solution: according to the solubleness of FNSH preparation 500ml saturation ratio is 45 ℃ growth solution, at the K of 500ml ₉It is 44 ℃ that ground glass is educated in the brilliant bottle with hanging the saturation point that brilliant method records solution.With the filtering with microporous membrane solution of 0.25 μ m, 55 ℃ were descended 24 hours postcooling to 45 of hot solution ℃, and the pH value of solution is 2.5.

3. the preparation of seed crystal: pick out more transparent complete 5mm in the small-crystalline that the cooling nature is separated out from saturated solution ³About the FNSH small-crystalline as seed crystal, tie with hairline, be fixed on the glass crystal dwang by plastics tubing, put into the above-mentioned saturated solution rotation growing crystal of lowering the temperature after the preheating.

4. crystal growth: the temperature-controlled precision of crystal nourishing jar is ± 0.01 ℃, and crystal rotating rotating speed is 50 rev/mins, 0.4 ℃/day of average cooling rate.Crystal (001), the average speed of growth of (110) and (100) face are 1.67,1.67 and 2.1mm/ days.Growth cycle through 15 days obtains 25 * 25 * 32mm ³The transparent FNSH monocrystalline of deep green.

Claims (3)

1. be used for ten sulfate dihydrate ferronickel crystal of ultraviolet and blue green color passband wave filter, it is characterized in that this crystalline molecular formula is FeNi (SO ₄) ₂12H ₂O, molecular weight are 522.87, belong to oblique system, spacer P2 (1)/c, a=9.994 (2) , b=7.2444 (14) , c=24.254 (5) , β=98.83 (3) °, V=1735.5 (6) ³, z=4, Dc=2.001gcm ^-3

2. the ten sulfate dihydrate ferronickel crystalline growth methods that are used for ultraviolet and blue green color passband wave filter of a claim 1 is characterized in that this crystalline growth temperature is 65 a ℃-room temperature; The temperature-controlled precision of growth groove is ± 0.01-0.02 ℃; The pH that regulates growth solution with sulfuric acid is 1.5-2.5; The crystalline velocity of rotation is at 30-60 rev/min; Each crystal face of crystalline (001), the average speed of growth of (110) and (100) face normal was controlled at 1-3mm/ days; Crystal growth cycle 0.5-1 month.

3. the ten sulfate dihydrate ferronickel crystalline that are used for ultraviolet and blue green color passband wave filter of a claim 1 are used, and it is characterized in that this crystal is used for the bandpass filter and the transmitter of UV-light and blue green glow.

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