Porcelain products and methods

A heat sinterable porcelain powder mix and a method of preparing a sintered porcelain product of desired color, particularly for use in the fabrication of dental appliances, which mix comprises an admixture of a porcelain powder with an organic liquid binder, which binder has an index of refraction the same or substantially the same as the index of refraction of the porcelain powder, thereby permitting visualization of the true post-sintered color of the porcelain powder mix during application and prior to heat sintering.

 

What is claimed is:

1. A premixed gel-like porcelain powder mix composition for use in the preparation of sintered porcelain products, which mix composition comprises:

(a) a porcelain powder; and

(b) an organic liquid binder admixed with the porcelain powder, the organic liquid binder having an index of refraction about the same as the index of refraction of the porcelain powder, to permit visualization of the true post-sintered color of the porcelain powder prior to heat sintering of the mix composition, the organic liquid binder consisting essentially of a material selected from the group consisting of:

(i) aryl-substituted alkanol,

(ii) alicyclic alcohol,

(iii) aryl alcohol,

(iv) alkyl ester of aryl acid,

(v) aryl ester of alkyl acid,

(vi) acyl-substituted alicyclic ketone,

(vii) alicyclic ketone,

(viii) benzyl ethyl ether,

(ix) diaryl ether,

(x) terpenoid alcohol,

(xi) tertiary aliphatic alcohol,

(xii) branched chain aliphatic keto alcohol,

and combinations thereof.

2. A premixed gel-like porcelain powder mix composition for use in the preparation of sintered porcelain products, which mix composition consists essentially of:

(a) a porcelain powder; and

(b) an aryl-alkyl ether as a liquid organic binder and admixed with the porcelain powder, the aryl-alkyl ether having an index of refraction about the same as the index of refraction of the porcelain powder to permit visualization of the true post-sintered color of the porcelain powder prior to heat sintering of the mix composition.

3. The composition of claim 1 wherein the orgnanic liquid binder has an index of refraction of from about 1.49 to 1.56.

4. The composition of claim 2 wherein the alkyl-aryl ether is benzyl ethyl ether.

5. The composition of claim 1 wherein the organic liquid binder comprises a mixture of a benzyl-containing alcohol and an alicyclic alcohol.

6. The composition of claim 5 wherein the benzyl-containing alcohol comprises benzyl alcohol or a benzyl-substituted alkanol.

7. The composition of claim 5 wherein the alicyclic alcohol comprises cyclohexanol or cycloheptanol.

8. The composition of claim 5 which includes benzyl ethyl ether.

9. The composition of claim 5 wherein the benzyl-containing alcohol comprises from about 80 to 99 percent by volume of the organic liquid binder.

10. The composition of claim 1 wherein the organic liquid binder comprises a mixture of benzyl-substituted tertiary-butanol and cycloheptanol.

11. The composition of claim 10 which mixture includes benzyl ethyl ether.

12. The composition of claim 1 wherein the organic liquid binder comprises from about 10 to 50 percent by weight of the mix composition.

13. The composition of claim 1 wherein the porcelain powder is essentially free of an organic dye.

14. The composition of claim 1 wherein the organic liquid binder is selected from the group consisting of: benzyl acetate; benzyl-tert-butanol; ethyl benzoate; phenyl acetate; 2-acetylcyclohexanone; cycloheptanol; cyclohexanol; benzyl alcohol; 4-hydroxy, 4-methyl, 2-pentanone; benzyl ethyl ether; nerol; phenethyl alcohol; cyclohexanone; tert-amyl alcohol and combinations thereof.

15. A premixed gel-like porcelain powder mix composition for use in the preparation of dental appliances, which mix composition comprises:

(a) a dental porcelain powder; and

(b) an organic liquid binder admixed with the dental porcelain powder, the organic liquid binder comprising a mixture of a benzyl-substituted alkanol and an alicyclic alcohol, which mixture has an index of refraction of about 1.49 to 1.56 which is the same or substantially the same index of refraction of the dental porcelain powder to permit visualization of the true post-sintered color of the porcelain powder prior to heat sintering the mix composition to fabricate the dental appliance.

16. The composition of claim 15 wherein the alkanol comprises benzyl-tertiary-butanol.

17. The composition of claim 15 wherein the alicyclic alcohol comprises cycloheptanol or cyclohexanol.

18. The composition of claim 15 wherein the mixture includes benzyl ethyl ether.

19. The composition of claim 15 wherein the organic liquid binder has an index of refraction of about 1.49 to 1.51.

20. A method of preparing a gel-like porcelain product mix of the desired color, which method comprises:

(a) admixing together a sinterable porcelain powder and a liquid binder, which liquid binder is selected to have an index of refraction about the same as that of the porcelain powder, to provide a heat sinterable porcelain powder mix, the liquid binder consisting essentially of a material selected from the group consisting of:

(i) aryl-substituted alkanol

(ii) alicyclic alcohol,

(iii) aryl alcohol,

(iv) alkyl ester of aryl acid,

(v) aryl ester of alkyl acid,

(vi) acyl-substituted alicyclic ketone,

(vii) alicyclic ketone,

(viii) aryl-alkyl ether,

(ix) diaryl ether,

(x) terpenoid alcohol,

(xi) tertiary aliphatic alcohol,

(xii) branched chain aliphatic keto alcohol,

and combinations thereof;

(b) visually observing the color of the heat sinterable mix prior to heat sintering the mix, to determine true post-sintered color; and

(c) adjusting the color or shading, if required, of the heat sinterable mix prior to heat sintering to that color or shading desired in the post sintered product based on such visual observation.

21. The method of claim 20 wherein the porcelain powder comprises a dental porcelain powder suitable for use in the construction of dental appliances.

22. The method of claim 20 wherein the liquid binder comprises a mixture of a benzyl-containing alcohol and an alicyclic alcohol.

23. The method of claim 20 wherein the liquid binder comprises an organic liquid mixture of a benzyl-substituted branch alkanol and a C.sub.5 -C.sub.7 cycloaliphatic alcohol.

24. The method of claim 20 wherein the liquid binder comprises an organic liquid mixture of a benzyl-substituted tertiary butanol and cycloheptanol.

25. The method of claim 24 wherein the liquid composition binder is admixed in a ratio by volume of 20 parts of the benzyl-substituted butanol to 1 part of cycloheptanol.

26. The method of claim 20 wherein the index of refraction of the liquid binder ranges from about 1.49 to 1.56.

27. The method of claim 20 which includes:

(a) employing a dental porcelain powder containing an organic dye;

(b) heating the dental porcelain powder prior to admixing to remove the organic dye; and

(c) admixing the dye-free dental porcelain powder with the organic liquid binder.

28. The method of claim 20 which includes:

(a) applying the heat sinterable porcelain mix onto a substrate after any adjustments required for proper color and shading; and

(b) heat sintering the substrate and applied porcelain mix to obtain the heat sintered product of the selected color or shading.

29. The method of claim 20 wherein the organic liquid binder is characterized by an index of refraction of from about 1.49 to 1.51.

30. The method of claim 20 wherein the liquid binder comprises a miscible admixture of two or more organic liquids and which liquid binder has an index of refraction of about 1.45 to 1.60.

31. The method of claim 20 which includes:

(a) heat sintering the color adjusted porcelain powder mix; and

(b) recovering the heat sintered porcelain product.

32. The method of claim 20 wherein the liquid comprises an organic liquid binder which contains benzyl alcohol or a benzyl-substituted alkanol.

33. The method of claim 20 which includes:

(a) applying the sinterable porcelain powder mix onto a substructure;

(b) adjusting, if necessary, the color or shading of the mix to that of a portion of the substructure; and

(c) heat sintering the substructure and the applied porcelain powder mix to obtain a sintered product of the desired color or shading.

34. The heat sintered porcelain powder product produced by the method of claim 31.

35. The heat sintered product produced by the method of claim 33.

36. A method of preparing a heat sintered porcelain dental appliance for use in the oral cavity, and which dental appliance will have the desired color and shading, which method comprises:

(a) admixing together a dental porcelain powder with an organic liquid binder, which organic liquid binder comprises a mixture of a benzyl tertiary butanol and cycloheptanol, to provide a heat sinterable porcelain dental mix, which liquid binder is characterized by an index of refraction which is about the same as the dental porcelain powder;

(b) applying the dental mix to a substrate;

(c) visually observing the color of the dental porcelain powder mix prior to heat sintering to form the dental applicance;

(d) adjusting the color or shading, if required, of the heat sinterable mix as desired in the post-sintered dental appliance product;

(e) heat sintering the heat sinterable dental porcelain mix; and

(f) recovering the heat sintered porcelain dental appliance having the selected color or shading as prior to heat sintering.

37. The composition of claim 1 wherein the organic liquid binder comprises a mixture of a diaryl ether, benzyl tertiary butanol and cycloheptanol.

38. The composition of claim 1 wherein the aryl ester of an alkyl acid comprises an aryl acetate.

39. The method of claim 36 wherein the organic liquid binder includes benzyl ethyl ether.

40. The heat-sintered dental appliance produced by the method of claim 36.

41. The composition of claim 1 wherein the porcelain powder comprises a porcelain powder for use in the fabrication of dental devices.

42. The composition of claim 2 wherein the porcelain powder comprises a dental porcelain powder for the fabrication of dental devices.

43. The composition of claim 2 wherein the aryl-alkyl ether has an index of refraction of from about 1.4 to 1.6.

BACKGROUND OF THE INVENTION

Ceramic powders have been utilized in dentistry for artificial teeth since the eighteenth century (Alexis Duchateau and Dubois de Chemat) and for fixed restorations (crowns) since the late ninteenth century, (Dr. Charles H. Land). Porcelain powder for use by dentists and dental technicians for the building-up and shaping of dental appliances such as crowns, bridges, and artificial teeth are well known (see for example U.S. Pat. No. 3,400,097). Recent advances in technology have led to widespread use of porcelains fused to various metals and other substructures such as crystalline ceramics. The various techniques involved in the use of porcelains for dental restorations all make use of a liquid binder to hold porcelain particles together to allow the powder to be built and shaped to the desired tooth form. After condensing and shaping the liquid binder is removed from the mass usually by heat and the porcelain mass sintered.

The most common liquid binder used in dentistry is distilled water. Some manufacturers have tried additions of glycerine, propylene glycol or alcohol. Most additives are used to slow the drying process thus increasing the working time of the mix. Daskalon et al (U.S. Pat. No. 3,880,662, issued Apr. 29, 1975 hereby incorporated by reference) addressed this problem by substitution of part or all of the distilled water with water miscible polyhydric alcohols and ethers of alcohols. The usual procedure of shaping dental porcelain, however, remained to mix the dry powder with distilled water to a thick and creamy consistency and then apply it to the substructure (usually metal) with either a brush or spatula. The water is then withdrawn by wicking which causes the powder particles to pack more closely. This condensation of particles allows the mass to be shaped by carving. Keeping the mass moist during buildup is critical, since the powder can dry out rapidly and further placement of porcelain on a dry surface does not allow the understructure to be condensed properly. Restorations baked in such a way are more subject to air entrapment and can appear blotchy and opaque.

Proper application of porcelain powders is critical in constructing dental appliances and requires great skill not only for proper condensation, but also for correct development of color. The ceramist is required to place various shaded powders in order to achieve desired gradations of color and translucency in the finished product. This must be accomplished without seeing the true shades and modifications until the porcelain mix is sintered or vitrified. This requires great skill and imagination. Some dental porcelain manufacturers have tried to facilitate this process by the addition of organic dyes to allow differentiation of the blends of the various powders during the buildup. However, these colorants are arbitrary and bear no relation to the sintered shades.

SUMMARY OF THE INVENTION

The invention relates to liquid binders for use with porcelain powders to prepare heat sinterable porcelain mixes, to the porcelain mixes so prepared and to the method of preparing and fabricating sintered objects of desired color. In particular the invention concerns an organic liquid binder for use with dental porcelain powders and to the dental mixes prepared thereby, which liquid binder permits visualization of the true post-sintered color of the dental porcelain powder mix during application and prior to heat sintering to fabricate the dental appliance.

The invention relates to the use of organic liquid binders with porcelain powders and particularly dental porcelain powders to prepare sinterable porcelain mixes and which liquid binder allows visualization of the true post-sintered colors of the porcelain powders during application of the sinterable mix and prior to heat sintering of the mix. The organic non-aqueous liquid binder of the invention does not dry out under normal working conditions and possesses adhesive and cohesive properties conducive to the proper buildup when employed as an organic binder with porcelain powder. The liquid binder should have proper surface tension to permit wetting of the substructure in the fabrication of dental appliances and forms a gel-like mix with the porcelain powders minimizing hydraulic classification of the powder particles during condensation. The organic liquid binder also permits the dental porcelain powder mix to be supplied or stored in single packages or containers in a premixed state ready for use by the dentist or dental technician or ceramist and with actual color visualization of the post-sintered porcelain. At present dental porcelain powders and the distilled water or glycerine-water for mixing are supplied in separate containers and must be mixed immediately prior to use.

The present invention simplifies the buildup procedure in the construction of dental appliances and other ceramic products in two major ways. In the first way a liquid binder is used with slower volatilization so that the wet powder mix does not dry out during the buildup process. The mix can remain moist and workable until force dried. This decreases the skill required and allows interruption of work with no detrimental affects. In the second way by adjustment of the index of refraction of the liquid binder to match the index of refraction of the porcelain powder the true colors and shading of the mix can be visualized at the time of buildup and not only at or after the sintered stage. This represents a tremendous advantage to the ceramist as the color and shading modifications can be seen prior to sintering. This advance permits the artistic abilities of the ceramist, such as in the fields of art, industry, and dentistry to be better realized while requiring less skill in the fabrication of sintered porcelain products.

The liquid binders which constitute the present invention are single organic liquids or mixes of miscible organic liquids which have appropriate dispersivity and an index of refraction of the base glass frit used in porcelain powder such as a dental porcelain powder. These properties minimize light scattering by the particles of base glass and thus permit visualization of the true post-sintered color inherent in the porcelain powder composition during application and before firing or sintering. The organic liquid should also have the proper surface tension to allow wetting of the substructure and a suitable boiling point to allow evaporation of all the liquid prior to attainment of porcelain sintering temperatures. In addition, the liquid and its vapors should leave no residues that might react at firing temperatures and thus alter the properties of the base glass. The boiling point, index of refraction, dispersivity and rheologic properties are controlled by proper combination of the organic components in the liquid binder. A proper liquid binder also exhibits adhesive properties to the substrate and cohesive properties facilitating handling and buildup. Also by forming a gel-like mix with the porcelain powder, the organic liquid binder prevents hydraulic classification of the powder particles during condensation which can be a problem with existing aqueous compositions used with dental porcelain powders.

Various organic liquids may be used as the organic liquid binder in the invention either alone or in various combinations and typically such organic liquids so employed have a boiling point of over about 100.degree. C. such as from about 110.degree. to 144.degree. C./85 mm Hg. Generally, the liquid binder has a refractive index which various from about 1.4 to 1.6 and more typically around 1.49 to 1.56, such as 1.49 to 1.51. Thus, an individual organic liquid for use with present commercial dental powders may be employed where the liquid provides for the right index of refraction to match that of the porcelain powder to be employed or more commonly a combination of organic liquids is employed.

A wide variety of organic liquids may be used in various miscible proportions, such as for example, but not to be limited to: aryl-substituted alcohols such as the benzyl-substituted branched chain alcohol such as benzyl-substituted alkanols and more particularly the benzyl-tertiary-butanol or other similar carbinol-type liquids, alicyclic alcohols, and more particularly C.sub.7 -C.sub.6 alicyclic alcohols such as cycloheptanol and cyclohexanol, aryl alcohols, alkyl esters of aryl acids, aryl esters of alkyl acids, acyl-substituted alicyclic ketones, alicyclic ketones, aryl-alkyl ethers, diaryl ethers, terpenoid alcohols, tertiary aliphatic alcohols, and branched chain aliphatic keto alcohols.

The organic liquid binder useful particularly with dental porcelain powder whether as a single organic liquid binder or an organic liquid binder composed of two, three, four or more liquids generally requires at least one liquid to have an aryl, e.g. a benzyl or phenyl group or an alicyclic group in order to obtain the necessary index of refraction. The liquid binder may comprise a single liquid such as an aryl alkyl ether like benzyl ethyl ether. Liquid binders which contain two or more liquids often include an aryl-containing alcohol such as a benzyl-substituted alkanol like benzyl-tertiary-butanol or benzyl alcohol. Other components may include, alone or in combination with the aryl-containing alcohols, alicyclic alcohols, aryl acetates, acyl alicylic alcohols, benzyl ethyl ether, terpenoid alcohols, pentanones, etc. Some specific organic liquids useful, alone or in combination, include, but are not limited to: benzyl acetate; benzyl-tertiary-butanol; ethyl benzoate; phenyl acetate; 2-acetylcyclohexanone; cycloheptanol; cyclohexanol; benzyl alcohol; 4-hydroxy, 4-methyl, 2-pentanone; benzyl ethyl ether; nerol; phenethyl alcohol; cyclohexanone and combinations thereof.

Although various combinations of organic liquids may be used, a preferred organic binder is composed of a mixture of a benzyl-tertiary butanol (also known as phenylethyl dimethyl carbinol) and cycloheptanol which forms an organic solution having an index of refraction of 1.5068 at 25.degree. C. and is suitable for use with most commercially available dental porcelain powders when employed in a ratio of 20 parts by volume of the benzyl-tertiary-butanol and one part by volume of the cycloheptanol. Another preferred organic liquid binder comprises 19 parts by volume of benzyl-tertiary-butanol, 1 part by volume cycloheptanol, and 20 parts by volume of benzylethyl ether with an index of refraction of n.sub.D.sup.25.degree. C. of 1.5002. These ratios provide: a proper surface tension and thus wetting of the substructure in the fabrication of a dental appliance; optimum rheological properties for forming; and optimum optical properties for the true color and shading visualization of the sinterable porcelain powder mix prior to sintering of the mix. If desired, various diluents to modify the handling properties of the mix may be used such as hydrocarbon esters, ketones, acids, alcohols, ethers, and the like in varying amounts. In addition, various soluble additives may be incorporated in the organic liquid binder if desired including stabilizers, antioxidants, diluents, surfactants, dispersing agents, and other additives in minor amounts as desired provided such additives do not interfere with the function of the organic binder or prevent the true color visualization prior to sintering.

The ratio of the organic liquids used in the liquid binder may vary so that the resulting liquid binder has the desired index of refraction. For example, where a benzyl-substituted alkanol is employed as one component and a alicyclic alcohol as another component the alkanol is typically employed in an amount from 80 to 99 percent by volume and more typically 90 to 98 percent by volume.

The liquid binders of the invention are usefully employed with a wide variety of porcelain powders to include and not be limited to dental porcelain powders employed for the purposes of fabricating dental appliances such as crowns, fixed bridges, artificial teeth and the like on a substructure or alone and as well as porcelain or particulate-type powders employed in other fields such as the fabrication of china, industrial ceramics, tile or other materials formed from porcelain powders or refractories where it is desired to provide a accurate color or shading in the resulting product. This would include metallo-porcelain art constructs.

Typically porcelain powders are comprised of one, or more commonly, a plurality of sinterable or vitrifiable metal oxides such as oxides of aluminum, magnesium, silicon, boron, or alkali metal or alkali earth metal such as sodium, potassium, calcium and the like, as well as silicates and phosphates. Such porcelain powder mixtures may also include other ingredients such as pigments, clays, binders, metal salts such as oxides for tint and color, and dyes. A typical dental porcelain powder may comprise a combination of aluminum oxide, silicon oxide, boron oxide, as well as potassium and sodium oxide. These powder mixtures are reacted at elevated temperatures to form a vitreous material which is ground to form a dental porcelain powder.

The amount of the liquid binder to be employed with the porcelain powders may vary as desired to provide the desired paste or gel-like consistency to form the object to be sintered, but usually, the organic liquid is used in amounts from about 10 to 50 percent by weight and more typically about 18 to 35 percent by weight of the total organic liquid and porcelain powder mix. The sinterable porcelain mix is prepared by admixing at room temperature the porcelain powder with the organic liquid.

The invention will be described for the purposes of illustration only in connection with certain embodiments; however, it is recognized that various changes, modifications, and improvements to these illustrative embodiments may be made by those persons skilled in the art all falling within the spirit and scope of the invention. The embodiments will be described in connection with the preparation of dental appliances; however, it is recognized that the invention will find use in industrial and/or "artistic" ceramics and other fields where true color visualization and shading is desirable prior to sintering.

DESCRIPTION OF THE EMBODIMENTS

Various commercially available dental porcelain powders were mixed with the organic liquid binders and the pre- and post-fired colors compared. All commercially available porcelain powders tested were found to work well with the organic liquid binders to achieve the desired result. If a commercial dental porcelain powder were encountered with an index of refraction so different from the norm that the described liquid did not provide true color visualization before firing, the index of the organic liquid is readily adjusted, such as by the addition of other liquids or a change in composition to accomodate the index of refraction of the porcelain powder. The commercially available dental porcelain powders fall into two groups, those with organic dyes to help differentiate the layers of porcelain during buildup and those with no organic dyes present. An example of the use of each type is given.

EXAMPLE 1

A commercial dental porcelain powder with no organic dye colorants such as Cerestore.TM. veneer (Johnson and Johnson Dental Products Company) is thoroughly mixed with a liquid binder of benzyl-tertiary-butanol and cycloheptanol (volume ratio of 20 to 1) to a paste or thick gel-like consistency which is easily lifted with a brush or small spatula. A ratio of approximately 1 gram of porcelain powder to 0.3 ml of the liquid binder gives the desired mix. The organic liquid binder had an index of refraction of n.sub.D.sup.25.degree. C. of 1.5068 which is the same or substantially the same as the porcelain powder used in the mix. The mix is then applied to the alumina substrate of the Cerestore.TM. system in small increments. The mass is then alternately blotted with an absorbent tissue and vibrated to condense the powder mass as is done with the conventional techniques employing aqueous binders. Slumping during the procedure is considerably less than by comparison with a conventional porcelain-water mix and the technician has extended working time. With the liquid binder the porcelain powder can be premixed with the organic liquid binder and stored in containers ready for subsequent use.

The porcelain paste demonstrates the same shade prior to forced dryout and firing as in the post-fired crown.

After application of the various shaded porcelains the restoration is then dried, as in the conventional approach, by placing it in front of the open door of a furnace muffle for five to ten minutes depending on the size of the appliance. The restoration should completely dry out and turn chalky white before firing. It is then fired according to the particular manufacturer's recommendation to achieve vitrification. After removal from the furnace and cooling, the restoration will demonstrate the same color as the predried, prefired buildup.

EXAMPLE 2

A commercial dental porcelain powder such as Vita VMK 68 (Vident) which contains organic dyes for distinguishing blends of powders is first heated to 1000.degree. F. for approximately 10 minutes to burn off the organic dyes. The resultant white powders are then mixed with the organic liquid binder and utilized as in Example 1. The actual metal oxide colorants incorporated by the manufacturer are visualized at the buildup stage when the gel-like mix is applied to the metal substrate in the case of ceramo-metal restorations or to platinum foil in the case of jacket crown restorations. This feature makes it easier for the technician to blend body and incisal portions of a tooth which is presently difficult and often done in two separate bakes. The liquid binder's capability of disclosing actual color of the fired porcelain before sintering also facilitates any necessary secondary firings, because further additions to the fired crown will have the appearance of the fired portion allowing the technician to realize the final effect on the shade of any modifications prior to additional bakes.

EXAMPLE 3

Example 1 was repeated employing as the organic liquid binder the following:

(a) Benzyl Acetate (1 vol)+and Benzyl-tert-butanol (1 vol)

n.sub.D.sup.25.degree. =1.5027

(b) Ethyl Benzoate 1 vol+Benzyl-tert-butanol 1 vol

n.sub.D.sup.25.degree. =1.5047

(c) Phenyl Acetate 1 vol+Benzyl-tert-butanol 1 vol

n.sub.D.sup.25.degree. =1.5021

(d) 2-Acetylcyclohexanone 4 vol+cycloheptanol 1 vol

n.sub.D.sup.25.degree. =1.4865

(e) Cyclohexanol 3.12 vol+Benzyl Alcohol 1.88 vol

n.sub.D.sup.25.degree. =1.4905

(f) 4-hydroxy, 4-methyl, 2-pentanone 1.94 vol+Benzyl Alcohol 3.06 vol

n.sub.D.sup.25.degree. =1.4938

(g) Cycloheptanol 1.94 vol+Benzyl Alcohol 3.06 vol

n.sub.D.sup.25.degree. =1.4911

(h) Benzyl ethyl ether

n.sub.D.sup.20.degree. =1.4955

(i) Benzyl-tert-butanol 1.17 vol+nerol 0.83 vol

n.sub.D.sup.24.degree. =1.4948

(j) Nerol 1.24 vol+Benzyl Alcohol 0.76 vol

n.sub.D.sup.23.degree. +1.4986

(k) Benzyl-tert-butanol 19 vol+Cycloheptanol 1 vol+Benzyl ethyl ether 20 vol

n.sub.D.sup.23.degree. +1.5002

(l) Phenethyl alcohol 1.15 vol+Cyclohexanone 0.85 vol

n.sub.D.sup.20.degree. +1.5000