Patent Publication Number: US-3874923-A

Title: Modified ferromagnetic chromium dioxide composition and method of preparing the same

Description:
Montiglio et a1.  
 MODIFIED FERROMAGNETIC CHROMIUM DIOXIDE COMPOSITION AND METHOD OF PREPARING THE SAME Inventors: Ugo Montiglio, Pierfrancesco Aspes; Giampiero Basile, Alessandria, both of Italy Assignee: Montecatini Edison S.p.A., Milan,  
 Italy Filed: Apr. 11, 1973 Appli No.: 350.033  
 Foreign Application Priority Data [451 Apr. 1, 1975 [56] References Cited UNITED STATES PATENTS 3.371.043 2/1968 Hund et a1. 252/6251 3,547,824 12/1970 Mihara ct a1. 252/6251 3,767,580 10/1973 Kitamoto ct a1 252/6251 FOREIGN PATENTS OR APPLICATIONS 7.009.061 12/1970 Netherlands 252/6251 Primary Examiner-Jack Cooper Attorney, Agent, or FirmHubbe11, Cohen &amp; Stiefel [57] ABSTRACT Modified ferromagnetic chromium dioxide composition containing minor amounts of La, Y, Sr, Ba. or mixtures thereof. Said chromium dioxide is made by heating a mixture of Cri ,(CrO )-nH O wherein n is from 1 to 8, and La, Y, Sr, and/or Ba to 250 to 500C under a pressure of from about 80 to 1000 atmospheres of oxygen.  
 16 Claims, No Drawings MODIFIED FERROMAGNETIC CHROMIUM DIOXIDE COMPOSITION AND METHOD OF PREPARING THE SAME BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ferromagnetic chromium dioxide composition containing one or more suitable modifiers which renders the composition particularly useful for application in the field of magnetic recording, and to a method for preparing said composition.  
  2. Description of the Prior Art Chromium dioxide has found application in various aspects of magnetic recording, such as, in magnetic tapes for audio and video recordings, in computer tapes and computer memories, records, magnetic cards, etc. In some applications, for instance, video recording tapes, computers, and high fidelity audio recording, it is necessary that the chromium dioxide have special magnetic characteristics, such as, a coercive force of at least 300 Oersteds, (Oe), as high a sauration magnetization as possible, and a ratio of residual magnetization to saturation magnetization greater than 0.4. Moreover, the chromium dioxide should be made up of elongated particles having as uniform a length as possible. According to the prior art, ferromagnetic chromium dioxide may be obtained by thermal decomposition of chromyl chloride, CrO Cl or of CrO Using high pressures one can obtain a pure product, which product, however, has been shown to have poor characteristics both as regards magnetic properties (the coercive force is less than 200 Oe) and as regards granulometric properties, the particles being rather large, nonhomogeneous, and not appreciably elongated.  
 &#39; A chromium dioxide characterized by higher values of coercive force and by smaller and more elongated Nonetheless, even in these cases, the results obtained have not been altogether satisfactory, inasmuch as one generally does not obtain a sufficiently high coercive force (e.g., greater than 400 Oe) without at the same time decreasing the values of saturation magnetization and of residual magnetization. This is most probably due to the fact that the obtaining of high values for coercive force requires the use of larger quantities of modifier, with a resultant adverse effect or influence on the resulting ferromagnetic phase.  
  A previous patent application describes a method of obtaining a nonmodified CrO exhibiting good magnetic characteristics. In this method, rather than starting with ehromic anhydride, the starting material is hydrated chromium (III) chromate [i.e., Cr (CrO,,) .n- H O, wherein n may vary from 1 to 8], which is heated to a temperature of about 300 to 400C under a pressure of about 30 to 1,000 atmospheres.  
 SUMMARY OF THE INVENTION The present invention provides a new chromium dioxide composition characterized by high magnetic properties and by a high degree of particle uniformity. The invention further provides a method for obtaining such a chromium dioxide composition.  
  The novel composition of this invention comprises a chromium dioxide containing from 0.005 to 10 percent by weight of a modifier, namely, lanthanum, yttrium, strontium, barium, or mixtures thereof. V  
  The invention further comprises a process for obtaining the foregoing composition, which process comprises adding to hydrated chromium (III) chromate, i.e., Cr (CrO,) .nH O wherein n is from 1 to 8, from 0.005 to 20 percent by weight, based on the anhydrous salt (Cr (CrO of lanthanum, yttrium, strontium, and/or barium, either as such (metal form) or in the form of a metal compound thereof such as a metal oxide, a metal salt, or the like (such compound being added in a quantity such that the metal compounds or elements be in the percentage indicated with respect to the starting anhydrous chromium (Ill) chromate), and heating the resulting mixture to from about 250 to 500C under a pressure of from about to 1,000 atmospheres of oxygen. The resulting chromium dioxide composition contains from about 0.005 to 10 percent by weight of a modifier, i.e., lanthanum, yttrium, strontium, and/or barium, in the form of the metal oxide(s), and from about 55 to 62 percent by weight of chromium, which chromium is combined with oxygen, and consists of acicular particles of a tetragonal crystalline structure of the rutile type, having a length of up to 2,u., an average length generally of from 0.2 to 0.5;/., a length to width ratio of generally from 2:1 to 30.1 or even higher, and an average axial ratio of from about 4:1 to 8:1, which particles, under X-ray examination, show the same diffraction pattern as that of unmodified or pure chromium dioxide.  
  The coercive force of the above composition exceeds 280 Oersteds and may often attain a value greater than 400 Oersteds, and the saturation magnetization exceeds 60 electromagnetic units/gram and may attain a value of e.m.u./g. or even higher. The residual magnetization exceeds 25 e.m.u./g. and may attain a value of 50 e.m.u./g. or higher. This composition consists of particles of a single magnetic domain.  
 DESCRIPTION OF THE PREFERRED EMBODIMENTS The modifiers for obtaining the desired composition may be added to the initial chromium (III) chromate, either in their elemental form as previously indicated, or in the form of their oxides or other compounds thereof, for instance, their salts, such as halides, nitrates, sulfates, carbonates, oxalates, etc.  
  It has been observed, however, that the addition of a modifying element in the form of one of its salts may sometimes alter to some degree the characteristics of the chromium dioxide composition obtained, inasmuch as the anionmay exert an action of its own, albeit a generally slight action, which will superimpose itself on that of the cation of the modifying element. Thus, if one desires to eliminate any possibility of any such interference, it is preferable to add the modifying agent either in the form of an oxide or in its elemental form.  
  Although the above described modifiers may be added to the starting hydrated chromium chromate within wide proportions, it is obvious that there are preferred amounts which will vary depending upon the particular modifying clement. For La, the preferred quantity is from about 0.05 to 3 percent by weight. based on the anhydrous salt, Cr (CrO,) For Sr the preferred quantity is from about 0.2 to 3 percent by weight. For Ba the preferred quantity is from about 0.05 to 2 percent by weight. For Y, the preferred quantity is from about 0.1 to 3 percent by weight.  
  In the most preferred embodiment of this invention, the resultant chromium dioxide contains from 59.7 to 61.8 percent by weight of chromium and from 0.05 to 1 percent by weight of modifying elements. Such modified chromium dioxide consists of acicular and very homogeneous particles of a length less than 0.6 micron and generally from about 0.15 to 0.6;/., with an average length generally from about 0.25 to 0.4;/., and which show a length/width axial ratio of from about 3:1 to 30:1, with the average axial ratio generally being from about 5:1 to 8:1. The coercive force is greater than 350 Oersteds and may attain a value of 450 Oersteds or higher. The magnetization saturation is greater than 80 e.m.u./g. and may attain a value of 90 e.m.u./g. or higher. The residual magnetization is greater than 44 e.m.u./g. and may exceed 50 e.m.u./g.  
  The hydrated chromium (Ill) chromate, which serves as the starting material for obtaining the products of this invention, is a salt that may readily be obtained according to simple chemical reactions well known in the literature. (For a full review, see for instance, Gmelins Handbuch der Anorganischen Chemie, Verlag Chemie (1962), 8th Edition Chrom, Part B, pages 104-105.)  
  Hydrated chromium (lll) chromate is soluble in water and is shown to be amorphous under X-ray examination. Examination under infra red (I.R.) light shows a wide absorption band that starts at 9.5,u., reaches a maximum at 10.5u, and extends up to p.  
  A convenient method for obtaining hydrated chromium (Ill) chromate is by reduction of CrO with methyl alcohol in a stoichiometric quantity, according to the following reaction:  
  The resulting aqueous solution is evaporated under vacuum until attaining the desired content of water of crystallization.  
 To the chromium (Ill) chromate hydrate is then added the desired modifying agent. In order to obtain a suitable mixing of the substance, the chromium (Ill) chromate and the modifying agent may be intimately ground together in an agate mortar. A variant which frequently is preferable, because it ensures a still greater degree of uniformity of mixing and ultimately leads to a more homogeneous product, involves adding the modifying agent before evaporation of the chromium (lll) chromate solution resulting from the reduction of the CrO with alcohol. This system is particularly useful where the modifying agent is soluble in the aqueous chromium (III) chromate solution. In such case, in fact, the distribution of the modifying agent in the chromium (III) chromate proves to be completely homogeneous and, after reaction, will result in the most homogeneous product granulometry, with the product exhibiting the best magnetic characteristics.  
 Hydrated chromium (Ill) chromate, after addition of the desired modifying agent, is transformed into a fer-&#39; romagnetic composition of modified chromium dioxide, by heating in a suitable apparatus. One type of such apparatus is hereinafter described by way of example.  
  This apparatus consists essentially of an autoclave made of stainless steel or other suitable material, there having been placed in the autoclave, before starting the reaction, the hydrated chromium (111) chromate to which has been added the modifying agent.  
  The autoclave is provided with a first valve which, if desired, permits one to discharge the oxygen that is formed during the reaction, so that the pressure may be maintained at a constant value; a second valve for creating, before starting the reaction, the desired pressure by means of an external source of oxygen, and a manometer or pressure gauge for measuring said pressure. 1  
 A thermocouple, inserted into the reaction mass, en-  
 ables one to follow on a recorder the progression of the internal temperature in relationship with time.  
  The autoclave may be heated in a muffle furnace of suitable size, or in a chamber provided with hot gas circulation, or with other equivalent heating equipment. The temperature that is reached inside the autoclave at the end of the reaction is preferably from about 300 to 350C. The final pressure is preferably maintained at from about 200 to 400 atmospheres, though lower pressures, down to about 30 atmospheres, may also be used. Higher pressures, up to 1,000 atmospheres or more, while leading to the obtaining of the desired chromium dioxide, are unduly expensive and hence, although operable, are neither practical nor necessary. The characteristics of the modified chromium diox&#39; ide of the present invention were investigated as fol lows: By an X-ray diffractometer, inasmuch as CrO possesses a characteristic diffraction spectrum whose main reflections, defined for quantitative and qualitative analyses, are:  
 Relative Intensity about d=3.11 A 100 d=1.63A d=2.42A 60 By electron microscope examination, for instance, at  
 EXAMPLE 1 The chromium (III) chromate used as the starting material for obtaining the CrO- was prepared as follows:  
  2,000 g of CrO were dissolved in distilled water, and the volume of the solution was brought to 4 liters.  
  The solution was placed into a 4-nccked liter flask fitted with a stirrer, a reflux cooler and a thermometer.  
  To the solution were then added dropwise 160 cc of CI-I OH and the solution was then brought to boiling and kept boiling for about 6 hours. until the alcohol had reacted, being transformed into CO 10 cc were then drawn from the solution and on this sample the Cr /Cr ratio was determined by iodometric titration of the hexavalent chromium and by the determination of the total chromium after oxidation with Na O The ratio thus found was 1.5.  
  Then, 500 cc of the solution thus obtained were evaporated in a drier under vacuum, at 80C for 48 hours.  
  Thereby was obtained a dark brown vitreous-like mass, and the Cr &#34;&#39;/Cr was again determined and was shown to have remained unchanged. The water content was 10.7% (corresponding to 3 moles of H 0 per mole of Cr (CrO 1 10.7 g of the foregoing brown mass were ground in an agate mortar together with 0.5 g of lanthanum in the form of La o until complete homogenization was attained, and the granulometric size of the chromium chromate was 110p..  
  This chromium chromate/lanthanum oxide mixture was then poured into a 130 ml titanium test tube, which was then placed into an autoclave of the type previously described, made of stainless steel and having an internal volume of 240 ml.  
  In the air space between test tube and autoclave wall there were placed about 20 cc of distilled water.  
  The autoclave was heated in a muffle furnace maintained at a temperature of 380C. At the start, inside the autoclave there was established, by means of an oxygen bottle, a pressure of 85 atmospheres.  
  During the heating, the pressure inside the autoclave rose due to (1) the oxygen that was formed, (2) water evaporated, and (3) the effect of thermal expansion of the gases. After 4 hours, the interior of the autoclave reached a temperature of 330C, which temperature was then maintained for 130 minutes. The final pressure was to 360 atmospheres.  
 particles of a length of from 0.15 and 0.55 micron. with an average length of 0.35 and having an average length/width ratio of 7:1.  
  Analysis with a fluorescent X-ray spectrometer showed that lanthanum was present in an amount of 0.26 percent by weight of the product obtained. the remainder consisting of chromium (61.5%) and oxygen (38.24%, by difference).  
 The magnetic characteristics were as follows:  
 . 0 Oersteds Gauss cc/g By comparison, chromium dioxide obtained under the same conditions, but from chromium (Ill) chromate that had not been admixed with lanthanum oxide, showed the following characteristics: length of the particles between 0.1 to 06p. with an average length of O.27,u.and an average length/width ratio equal to 4:1.  
 The magnetic characteristics were as follows:  
  H,. 335 Oersteds 0&#39;, 86 Gauss cc/g (T /a3, 0.48  
 EXAMPLES 2-4 To each of three chromium chromate solutions obtained by reduction of CrO with Cl-l OH as described in Example 1, there was added La O in such amount that the solutions contained, respectively, 1%, 1.5%, and 2% by weight of lathanum based on the anhydrous 2( 4):;-  
  The three solutions were then evaporated under vacuum until attaining a content of crystallization water of 10% to l 1%.  
  After comminution in a mortar, the chromium chromate/lanthanum oxide mixture was treated in an autoclave under the same conditions as employed in Example 1.  
  The final pressures, the final temperature, the time during which the reaction mass was maintained at this final temperature, and the magnetic characteristics of the chromium dioxide products obtained are set out in After cooling, the pressure was released and the au- Table l hereinafter.  
 TABLE I REACTION CONDITIONS MAGNETIC CHARACTERISTICS Example La,% by Final Final Residence H 0&#39;, 03/0,  
 No. weight pressure. temperatime at atmospheres ture. C final temp- Oersteds Gauss erature, 1 cc/g min.  
 The CrO sample of Example 2 contained 0.33% of lanthanum.  
 EXAMPLES 5-6 To two Cr (CrO solutions obtained by the method described, in Example 1, by reduction of CrO; with CH OH, before evaporating to dryness, there were added, respectively, 1% oflanthanum (based on the anhydrous Cr (CrO present) in the form of La(NO and in the form of LaCl After evaporation there was attained a content of crystallization water corresponding to about 3 moles of water per mole of Cr- (CrO After comminution in a mortar, the mixture was reacted under the same conditions as described in Example l. The reaction conditions and the characteristics EXAMPLES 11-13 The following examples illustrate the characteristics of CrO modified with yttrium.  
 of the modified CrO obtained are set out in Table I1 Following the procedure described in Example 1, hereinafter. three samples of 110.7 g of Cr (CrO -,.3H O were TABLE II REACTION CONDITIONS MAGNETICAL CHARACTERISTICS Example Type of Final Final Residence H,. orr,/o-,,  
 No. Modifier Pressure. Temperatime at atms. ture, &#34;C final temp- Oersteds Gauss erature, cc/g min.  
 5 La(NO;il;r 365 340 210 340 87.1 0.44 (1 La(Cl);, 355 350 180 405 86.5 0.51  
 The (r(). of Example 6 contained 0.287: by weight of La.  
 EXAMPLES 7-l0 The following examples demonstrate the effect of the incorporation of strontium in CrO mixed in an agate mortar with respectively: 0.5 g, 1 g, and 2 g of yttrium in the form of Y O These mixtures were then reacted as described previously.  
 The reaction conditions and the magnetic character- Using the procedure of Examples 26, four solutions istics for the CrO products obtained are set out in of chromium (lll) chromate were prepared.  
 Table IV hereinafter.  
 TABLE IV REACTION CONDITIONS MAGNETIC CHARACTERISTICS Example Y added, Final Final Residence H,. Oersteds 03. 03/0,,  
 No. 71 by weight Pressure, Temperature. Time at Gauss atms. C Final Temp., min. ec/g The (r0 of Example 11 contained 0.1 171 by weight of yttrium.  
  To three of these solutions SrClwas added in such quantity that the respective percentages of strontium with respect to the anhydrous Cr (CrO were 0.5%, 1.0% and 1.88% by weight. To the fourth solution was added SrSO, in such amount as to provide 1% of Sr with respect to the anhydrous Cr (CrO present. The  
 solutions were then evaporated to a water content of 45 EXAMPLES 14-17 The following examples illustrate the use of barium as the modifier.  
  To four solutions of Cr (CrO.,) obtained by the reduction of CrO with CH OH according to the procedure described in Example 1, were added respectively, 0.5% by weight of barium based on the anhydrous chromate, in the form of Bacl 1.0% by weight of barium in the form of BaCl 2.0% by weight of barium in the form of BaCl and 1.0% by weight of barium in the form of BaSO After evaporation, grinding and reaction according to the previously described examples, the chromium dioxides obtained showed the magnetic characteristics reported in Table V hereinafter.  
 TABLE III REACTION CONDITIONS MAGNETIC CHARACTERISTICS Example Type of Sr, Final Final Residence H,. 0,, (T /0&#39; No. Modifier by Pressure, Temp. Time at in anhyatms. C Final Oersteds Gauss drous Temp., cc/g Cr min. l fla 7 SrCl: 0.5 365 330 200 360 87.4 0.49 8 SrCl 1 340 330 190 410 85.3 0.56 9 SrCl, 1.88 350 335 130 400 86.2 0.57 10 SrSO 1.0, 340 I 335 180 400 87.1 0.51  
 The CrO sample of Example 8 contained 0.25% by weight of strontium.  
 TABLE V REACTION CONDITIONS MAGNETIC CHARACTERISTICS Example Type of Ba. &#34;/1 by Final Final Residence H 0&#39;,- o&#39; la,  
 No. Modifier weight in anhydrous Pressure, Temperature. Time at Final C r (C r0 atmospheres C Temperature, Oersteds Gauss min. cc/g l4 l3aCl 0.5 350 300 200 390 85.9 0.52 BaCl 1.0 345 330 150 380 85.3 0.46 lo Batll 2.0 360 340 120 365 83.7 0.44 17 BaSO, 1.0 355 335 125 380 83.2 0.47  
 The barium content in the (r0 samples was as follows: Example 14 0.42% by weight; Example 16 1.53% by weight; Example 17 0.79% by weight.  
 EXAMPLES 18-19 ide of claim 1 comprising intimately admixing a hy- 15 drated chromium (III) chromate of the formula The following examples are given for comparative 2( i)s- 2 wherein is from 1 t0 with 21 modipurposes to illustrate the effect of known modifiers on fi r, ai modifier being present in an amount of from the magnetic characteristics of CrO obtained from ab0l t 0.005 to percent by weight of the anhydrous chromium (III) chromate. salt, Cr (CrO said modifier being selected from the To two samples of a Cr- (CrO solution obtained by 20 group consisting of lanthanum, yttrium, strontium, barthe reduction of CrO with CH OH according to the ium, their oxides, their salts, and mixtures thereof, and procedure described in Example 1, there were respecheating the foregoing admixture to a temperature of tively added 1% Sb, in the form of SbCl and 1% of Sn from about 250 to 500C under a pressure of from in the form of SnCl each based on the anhydrous about 80 to 1,000 atmospheres of oxygen.  
 Cr (CrO,);,. 25 3. The method of claim 2, wherein the modifier After evaporation until a content in crystallization which is admixed is lanthanum, lanthanum oxide, or a water of about 10% by weight was attained, and after lanthanum salt, and wherein the amount of modifier is communition in a mortar, the mixtures were reacted such as to provide from 0.05 to 3 percent by weight of under the same conditions as in the preceding eXamlanthanum, expressed as metal, based on the anhydrous ples. salt.  
  The CrO products obtained showed the magnetic 4. The method of claim 2, wherein the modifier characteristics set out in Table VI hereinafter. which is admixed is strontium, strontium oxide, or a TABLE VI REACTION CONDITIONS MAGNETIC CHARACTERISTICS Example Type of Final Final Residence H Oersted 0&#39;, er /0&#39;,  
 No. Modifier Pressure, Temperature, Time at Gauss atm. &#34;C Final Temperature, cc/g 18 SbCl 350 330 200 280 83.1 0.37 19 SnCl- 360 330 I80 285 84.3 0.40  
  As is clearly shown from Table VI, the known modifistrontium salt, and wherein the amount of modifier is ers of the prior art give a chromium dioxide composisuch as to provide from 0.2 to 3 percent by weight of tion that exhibits magnetic characteristics that are disstrontium, expressed as metal, based on the anhydrous tinctly inferior to those obtained when using the modisalt. tiers of the present invention. 5. The method of claim 2, wherein the modifier Variations can, of course, be made without departing which is admixed is barium, barium oxide, or a barium from the spirit and scope of the invention. salt, and wherein theamount of modifier is such as to Having thus described the invention, what is desired provide from 0.05 to 2 percent by weight of barium, ex-  
 to be secured by Letters Patent and hereby claimed is: pressed as metal, based on the anhydrous salt.  
  1.Amodified ferromagnetic chromium dioxide com- 6. The method of claim 2, wherein the modifier position, consisting of about to 62 percent by weight 55 which is admixed is yttrium, yttrium oxide, or an ytof chromium, said chromium being combined with oxytrium salt, and wherein the amount of modifier is such gen, and from about 0.005 to 10 percent by weight of as to provide from 0.1 to 3 percent by weight of yta modifier selected from the group consisting of lanthatrium, expressed as metal, based on the anhydrous salt. num, yttrium, strontium and barium, and mixtures 7. The method of claim 2 wherein said intimate adthereof in the form of the oxide(s), the balance being mixing is carried out in the solid state. oxygen, said composition being in the form of acicular 8. The method of claim 2 wherein said intimate adparticles having a length less than 2p. and an axial mixing is effected by adding the modifier to a solution length to width ratio greater than 2:1 and having a teof the chromium (III) chromate. tragonal crystalline structure of the rutile type; said 9. An element for magnetic recording comprising a composition having a coercive force greater than 280 65 nonmagnetic supporting material carrying bonded to it Oersteds, a saturation magnetization greater than 60 a magnetic track made of a ferromagnetic composition e.m.u./g and a residual magnetization greater than 25 of modified chromium dioxide as defined in claim 1. e.m.u./g. 10. The element of claim 9 wherein the modifier is 2. A method of making the modified chromium dioxlanthanum.  
 being in the form of acicular particles of a tetragonal crystalline structure of the rutile type, the particle length being less than 0.6a, and the particles having a length/width axial ratio between 3:1 and 30:1; said composition having a coercive force of at least 350 Oersteds, a saturation magnetization greater than e.m.u./g., and a residual magnetization greater than 44 emu/g.  
  15. The composition of claim 14 wherein the modifier is lanthanum.  
 16. The composition of claim 14 wherein the modifier is yttrium.  
 mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION l a tent No. 3, 874, 923 Dated April 1, 1975 Inventor(s) Ugo Montiglio et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 Title page, left side, under &#34;Inventors&#34;: &#34;Ugo Montiglio, Pierfrancesco Aspes; Giampiero Basile, Alessandria, both of Italy&#34; should read Ugo Montiglio, Pierfrancesco Aspes, Giampiero Basile; all of Alessandria, Italy Title page, left side, under &#34;Foreign Application Priority Data&#34;: &#34;23466/72&#34; should read 23466 A/72 Column 4, line 48: &#39;magnetifications, should read magnifications,  
 Column 6, line 33: &#34;lathanum&#34; should read lanthanum Signed and sealed this 10th day of June 1975.  
 (SEAL) Attest c.- MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks