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Clays and Clay Minerals, Vol. 26, No. 2, pp. 13%143, 1978.

CHARACTERIZATION OF THE PARTICLE SIZE AND THE CRYSTALLINITY OF CERTAIN MINERALS BY IR SPECTROPHOTOMETRY AND OTHER INSTRUMENTAL METHODS--II. INVESTIGATIONS ON QUARTZ AND FELDSPAR
J. HLAVAY, K. JONAS, S. ELEK AND J. INCZEDY Veszprem Universityof ChemicalEngineering,Veszprem, 8201 Hungary
(Received 22 June 1976)

Abstract--Infraredspectra of two minerals;Urkut quartz (Hungary)and a Swedishfeldspar, of differentoriginwith different physicalcharacteristicsand crystallinitywere studied. Sampleswere takenafter appropriategrinding,and infrared spectra, X-raypowderdiffractionand watervaporabsorptionmeasurementswere madealongwithelectronmicrographs. Quantitativeconclusionswere drawnfromchangesof particlesizeand the ratioof bandsof the SilO groupsand alsothe degree of crystallinityand changes of the particle size, respectively. Key Words~CrystaUinity,Feldspar, Grinding,Orthoclase, Quartz.

ence band was found in the infrared spectra of quartz and feldspar because all band intensities were changed by the action of grinding. Moreover, we cannot investigate the irregularities of the lattices along selected crystal axes, because quartz and feldspar are not layered minerals. Changes of the band intensity taken at 802 cm -1 as a function of the grinding time is shown in Figure 3. At the beginning, the absorption values considerably increase. After a certain grinding time (in our case 4 days) they pass a maximum, then decrease again. The explanation of this phenomenon was summarized in Part I. It is well known that in the infrared spectra of amorphous silica the symmetrical bending vibration of the S i - - O group taken at 695 cm -a is missing. As in the infrared spectra of crystalline quartz, the symmetrical stretching vibration of the Si--O group at 800 cm -a can be observed and the absorption ratio at A 800 cm-a/A 695 cm -a can supply valuable information on the degree of crystallinity of quartz (Nemecz, 1960). The ratio of the above-mentioned absorption bands as a function of EXPERIMENTAL the grinding time is shown in Figure 4. The ratio of these absorption bands increases conTwo minerals were examined: Urkut quartz (Hungary) and a Swedish feldspar (orthoclase). The Urkut siderably at first. Then after a certain grinding time only quartz contains about 0.5-1% w/w amorphous material a slight increase is observed. This is explained as foland the Swedish feldspar contains about 2% w/w quartz lows: at the beginning of the grinding the main process and other clay minerals as previously determined by X- is the decrease of the particle size (band intensities inray powder diffraction. All measurements were carried crease). Later, because of the crystallinity decrease the 695 cm 1band intensity decreases considerably and the out as described in Part I. 802/695 cm -a ratio increases. During the grinding period RESULTS AND DISCUSSION the completely amorphous silica state could not be The infrared spectra of Urkut quartz and Swedish reached. After l0 days of grinding the intensity of the feldspar are shown in Figures 1 and 2. Band assign- absorption band at 695 cm a could still be measured. ments are listed in Table 1. Band intensities were de- When the aggregation began, the grinding was not so termined by the baseline method and the characteristic efficient and the ratio did not change appreciably. Other absorption values were calculated. No internal refer- analytical measurements confirm the conclusions 139

INTRODUCTION Some problems of the quantitative analysis of minerals by infrared spectrophotometry were reported in Part I. It was stated that the intensity of the characteristic absorption bands of the kaolinites depends considerably on the shape and crystalline state of the particles, as well as on their actual chemical composition. Quantitative determination of quartz, by infrared spectrophotometry, in dust, soil, other silicates and powdered coal was reported by Larsen (1972), Smallwood (1963), Hlavay (1976) and Tuddenham (1960). It was established that accurate and reproducible determinations can be carried out only on samples of strictly identical particle size and crystallinity. No literature data was found relating to a quantitative infrared analysis of feldspar. In the present work infrared and X-ray spectra were recorded, as well as water vapor absorption and scanning electron microscopic measurements of the original samples and of those subjected to grinding, in order to reduce the particle size and the degree of crystallinity.

140 Quartz

Hlavay, Jonas, Elek, and Inczedy Feldspar

Clays and Clay Minerals

1400

1200

I000

800

700

600

,500

400

1400

1200

I000

800

700

600

500

400

cm-I

c m -I

Fig. 1. Infrared spectra of Urkut quartz. drawn from the infrared spectra. The amorphitization of the Urkut quartz was followed by observing the decrease in intensity of the X-ray powder diffraction peak at 3.346 A. Changes of this peak area as a function of the grinding time are shown in Figure 5. At the beginning of the grinding there is a large change, later followed by a slighter decrease in the curve, i.e. the amorphitization of the quartz is continuous. When quartz is ground, the aggregation only can be observed later, compared to the grinding of clay minerals (that is, the efficiency of the grinding and the decrease of particle size is more pronounced with the later clay). In this period of grinding the specific surface area of quartz considerably increases. After 4 days of grinding only a small increase can be observed (Figure 6). The reason behind this may be that quartz is a very hard and brittle mineral and grinding breaks it into smaller pieces, resulting in large changes in the infrared and X-ray spectra as well as in the specific surface area measurements. Similar curves were obtained on the Swedish feldspar. Changes of the two most characteristic absorption bands of the infrared spectra, at 735 and 570 cm -1, in the characteristic reflection peak area of the X-ray spectra, as well as changes of the specific surface area as functions of the grinding time can be seen in Figure 7. No characteristic absorption ratio characterizing the

Fig. 2. Infraredspectra of Swedishfeldspar. change of the crystallinity was found in the infrared spectra of the feldspar studied. The explanation of the forms of the curves may be the same as that of the quartz. The decrease of the particle size and the agglomeratization of the Swedish feldspar was followed by stereoscanning electron microscopic (SEM) measurements. The SEM photograph of the original Swedish feldspar, and that of feldspar ground for 10 days, are shown in Figures 8 and 9. Some

Lo 7E 08
o

p~ ~ o6

/
I
2

0.4

o.2

I
4

I
6

I
8 I0

Grinding 'rime,

doys

Fig. 3. Changes of the band intensityat 802 cm-1 (Urkut quartz).

Table 1. Band assignments of Urkut quartz and Swedish feldspar. Samples Quartz Wavenumber (cm- 1) 1175, 1100 802, 785 695 516, 470 1200-950 775, 735 570 538 648 Assignments Si--O asymmetrical stretching vibrations Si---O symmetrical stretching vibrations Si--O symmetrical bending vibrations Si--O asymmetrical bending vibrations Si--O asymmetrical stretching vibrations Si--O---A1 compounded vibrations Si--O symmetrical bending vibration Si--O asymmetrical bending vibration A1--O co-ordination vibration

Feldspar

Vol. 26, No. 2, 1978


7.0

Investigations on quartz and feldspar

141

E
6.0

5 y

--

)4,~X~

x~X"~"x~X~Xm~

Quartz

m 5. 0

4.0 03

~o

I
days

I0

~o

4 6 Grinding time,

I
days

Grinding time,

I0

Fig. 6. Specific surface area of Urkut quartz.

Fig. 4.

Changes of the absorbance ratio taken at A 800 cm-VA 695 cm-~ (Urkut quartz).

large a n d irregular u n g r o u n d f e l d s p a r particles b e a r i n g the c h a r a c t e r i s t i c f o r m s can b e r e c o g n i z e d in Figure 8. A t the beginning o f the grinding p e r i o d t h e s e large particles w e r e b r o k e n and the small p r i m a r y particles a d h e r e d to the larger, original particles t h e r e b y dec r e a s i n g the effect o f grinding. T h e n the aggregation a n d the d e g r e e o f c r y s t a l l i n i t y b e c o m e m o r e pron o u n c e d , as can b e s e e n in Figure 9. Similar to the kaolins m e n t i o n e d in Part I, w e h a v e a t t e m p t e d to establish correlations d e s c r i b i n g the particle size, the a b s o r p t i o n ratio calculated f r o m the inf r a r e d s p e c t r a and the loss in crystallinity c a l c u l a t e d f r o m the X - r a y s p e c t r a as f u n c t i o n s o f the grinding time,

A0.2

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,s o

% 54

6N
"~-'b 3.346 A* quartz

"+"'+

-gel
2

4 6 Grinding time,

8 days

I0

Grinding time,

days

Fig. 5. Changes of the reflection peak area (3.346 A) as a function of the grinding time.

Fig. 7. Changesof the absorption bands of the infrared spectra (735 and 570 cm-1); the reflectionpeak of the X-ray spectra and the specific surface area of the Swedish feldspar.

Table 2. Samples Urkut quartz d vs t d = doe-~ a = 0.237 do = 3.2 am d = doe-~ a = 0.147 do = 2.60/an

The correlation functions of quartz and feldspar. y vs d y = 0.228 d 2 + 7.0 x vs d x = 0.20d + 0.37 y vs x y = - 2 . 5 4 x 2 + 7.53

Swedish feldspar

x = 0.03 d 2"5 + 0.22

y, absorbance ratio calculated from infrared spectra (A 802 c m - V A 695 cm-0. x, degree of amorphism calculated from X-ray spectra.

142

Hlavay, Jonas, Elek, and Inczedy

Clays and Clay Minerals

Fig. 8. SEM photograph of the original Swedish feldspar. Fig. 9. SEM photograph of the Swedish feldspar after 10 days of grinding.

Vol. 26, No. 2, 1978

Investigations on quartz and feldspar

143

7.0

Quartz

6.5

6.0

Y
5.5
-

5.0

4.5

0.5

I.O

1.5

2.0

2.5

3.0

d,

/.~m

Fig. 10. Absorption ratio, y, vs. particle size, d, function.

as well as to determine the absorption ratio vs. amorphism. The appropriate equation was described in Part I. The particle size of the original and the ground samples was determined in Part I. The peak area at 3.346 A (101), the characteristic reflection of the quartz and the p e a k area at 6.463 ~ of the feldspar, were measured. The ratio of the peak areas of the original and the ground samples s e r v e as a measure of the loss of crystallinity. The correlation functions are listed in Table 2. N o correlation was found for the absorption bands of the infrared spectra of the feldspar. T h e r e f o r e characteristic a b s o r b a n c e ratios could not be calculated. The y vs. d (average particle size) function of the U r k u t quartz is shown in Figure 10. It can be seen that changes of the particle size result in c o n s i d e r a b l e change of the absorption ratio of the quartz. The correlation function is a parabolic one with an a s y m p t o t e at 7.0. This means that the values o f y calculated from the infrared spectra may not be larger than 7.0 if the particle size of the sample is bel.ow the 0.3 /xm limit. The relationship b e t w e e n the degree of a m o r p h i s m (x) calculated from the X-ray spectra and the particle

size (d) of the quartz is a linear function. The r e a s o n for this is that the quartz breaks into smaller pieces, decreasing the state of its crystallinity during the whole grinding period. T h e s e changes are proportional to the d e c r e a s e of the particle size. A parabolic function was found to exist b e t w e e n the y and x values of quartz. F r o m the shape of the function it can be c o n c l u d e d that the changes in crystallinity of the quartz can result in a considerable change of the absorption ratio taken at A 802 c m - V A 695 c m - L The x vs. d function of feldspar was calculated as a polynomial function. F r o m this function the particle size of the samples can be determined if the x values are known. In conclusion, we can state (similar to our earlier observations m a d e in connection with kaolins, Part I), that if the particles are below the two micron size limit, the infrared bands intensities of quartz and feldspar d e p e n d on the average particle size of the primary particles, on the crystalline state of the particles and on the m e c h a n o c h e m i c a l activation. REFERENCES Hlavay, J., Jonas, K., Elek, S. and Inczedy, J. (1977) Characterization of the particle size and the crystallinity of certain minerals by infrared spectrophotometry and other instrumental methods. Part I. Investigations on clay minerals: Clays & Clay Minerals ~$, 451-456. Hlavay, J., Inczedy, J. and Stefanovits, P. (1975) Characterization of genetically different soil types by infrared spectrophotometry: Agrochem. Soil Sci. 24, 395-404. Larsen, D. J., Doenhoff, L. J. and Crable, J. V. (1972) The quantitative determination of quartz in coal dust by infrared spectroscopy: J. Am. Ind. Hyg. Ass. 33, 367-372. Nemecz, E. and Rethy, K. (1961) Investigation of silicate materials by infrared spectroscopy: Rep. Veszp. Univ. Chem. Engng. 5, 287301. Smallwood, S. E. and Hart, P. B. (1963) Thallous bromide as a disc material in infrared absorption spectroscopy: Spectrochim. Acta 19, 285-291. Tuddenham, V. M. and Lyon, R. J. P. (1960) Infrared techniques in the identification and measurements of minerals: Anal. Chem. 32, 1630-1634.

P e 3 m M e - H 3 y q a n H c b H H ~ p a K p a c H ~ e c n e K T p ~ ~ B y X M M H e p a n o B : K B a p ~ a Y p K y T /BeHF-phi/ M ~Be~CKOFO noneBoFo mnaTa, pasnMqHOFO npoHcxo~eHH~ c pasnHqHh~4M ~M3HqecKMMH CBO~CTBaMM H KpMcTa~HqHOCTbD. 06pa3~ 6511IH O T O 6 p a H ~ n o c ~ e H a ~ n e ~ai~ero H 3 M e ~ b q e H H R F H 3 & T e M n p o B e ~ e H ~ H 3 M e p e H H ~ M H ~ p a K p a c H ~ X CHeKTpOB,peHT-D e H O B e K M x c n e K T p O B , H O ~ y q e H H ~ X n o p o ~ K O B h l M M e T O ~ O M ~ H ~ p a K ~ M H r H H 3 M e p e H H H a6cOp6~MM BO~HOFO napa, O ~ H O B p e M e H H O C M 3 y q e H M e M M e T O ~ O M 9 n e K T p O H H O ~ MHKpo-F p a ~ H H . BBL~H H O ~ y q e H ~ K O ~ M q e C T B e H H ~ e ~ a H H ~ e 6 ~ a r o ~ a p ~ H 3 y q e H H D H S M e H e H H ~ p a s M e p O B q a C T H ~ H O T H O ~ e H H R c B H s e ~ F p y ~ H S i - 0 r a T a K ~ e C T e n e H M KpHcTanHqHOC-TH M C O O T B e T C T B y m m H X H 3 M e H e H H ~ p a s M e p a q a C T H U . K u r z r e f e r a t - I n f r a r o t s p e k t r a z w e i e r M i n e r a l i e n , U r k u t q u a r t z (Ungarn) u n d ein schwedischer Feldspat, von verschiedener Abstammung mit unterschiedlichen physikalischen Eigenschaften und Kristallformen wurden untersucht. Nach angemessenem Mahlen, wurden Proben genommen und Infrarotspektra, Rontgenpulverdiagramme, und Elektronenmikrographien aufgenommen und Wasserdampfabsorptionen gemessen. Von der Veranderung der TeilchengroSe, dem Verhaltnis der Schwingungen von den Si-0 Gruppen und auch dem Grad der K r i s t a l l i n i t ~ t , bzw. d e r V e r i n d e r u n g d e r T e i l c h e n g r o ~ e , w u r d e n q u a n t i t a tive Schlusse gezogen.