- Email: [email protected]
The diazotype process of photographic dyeing and printing
484
Chemical Section.
U. F. I.,
tion of lithium fluoride in a q u e o u s solution is a b o u t four calories less than the value which is d e d u c e d from Petersen's e x p e r i m e n t s on neutralization. T h e v a r i a t i o n s in the case of t h e o t h e r fluorides in the a b o v e table are so small that we m a y conclude that w e k n o w their true h e a t of formation w i t h i n the limits of e x p e r i m e n t a l error. T~E
D I A Z ( ) T Y P E P R O C E S S oF P H O T O G R A P H I C D Y E I N G AND P R I N T I N G . BY JOHN CARBUTT.
[Communicated to tke Ckemlca] Section, A1)ri! 2z, IS9z. ]
T h e s u b j e c t I have the p l e a s u r e to b r i n g before the Section this e v e n i n g is t h e " D i a z o t y p e P r o c e s s of Photographic D y e i n g a n d Printing," the d i s c o v e r y of Mr. Arthur G. Green, of London. It is a n e w m e t h o d of producing designs in fast colors on cotton, linen, silk, paper, etc., either from' hand-drawn designs on a t r a n s p a r e n t or semi-transp a r e n t medium, or b y u s e of a p h o t o g r a p h i c transparency. I t was first m a d e public at a m e e t i n g of the British Association for t h e A d v a n c e m e n t of Science, held at Leeds last September. I t is distinctly a positive process ; that is, it yields a positive from a positive. T h e o p e r a t i o n s are five in number, viz : dyeing, sensitizing, printing, d e v e l o p i n g and washing, corresponding v e r y closely in n u m b e r of o p e r a t i o n s required in preparing and p r i n t i n g on p a p e r b y the direct silver process of p h o t o g r a p h i c printing. P r i m u l i n e is t h e base of the new " d i a z o t y p e , " a n d is a l r e a d y in e x t e n s i v e use for dyeing calico in v a r i o u s tints: .Dyeing.--The first operation, then, is to dye our material with "primuline." T o do this t a k e ioo grains of "primuline," add to it t w e n t y o u n c e s of distilled w a t e r b r o u g h t to a boil in a flask over a B u n s e n b u r n e r ; w h e n d i s s o l v e d , pour into a porcelain dish, and i m m e r s e t h e fabric, cotton cloth (the cotton m u s t be free from dressing), or silk, and as soon as t h e piec, es seem t h o r o u g h l y i m p r e g n a t e d with the dye.
June, I89I. ]
Chemzcal Section.
485
remove and rinse in plain water, and squeeze as dry as possible, or place b e t w e e n sheets of b l o t t i n g paper. T h e fabric so p r e p a r e d h a s a p r i m r o s e hue, a n d so far is insensitive to light. 5"ensiti~zing. T h e second operation, or sensitizing, is accomplished b y i m m e r s i n g the dyed fabric in a solution formed of s o d i u m n i t r a t e sixty grains, cold w a t e r thirtytwo ounces, oxalic acid ~oo grains, previously dissolved in two ounces of water. E a c h piece is i m m e r s e d separately and soaked for two or three m i n u t e s , it is t h e n rinsed in water and dried. T h e color of the fabric s h o u l d be of a reddish-yellow hue, and is sensitive to l i g h t ; the operation should be p e r f o r m e d in a weak light, a n d the pieces dried in the dark. Pri~tting. Place in a p r i n t i n g f r a m e a glass transparency, and place over it a diazotized fabric in contact, and expose to d a y l i g h t t e n to t w e n t y m i n u t e s , or s u n l i g h t four to seven minutes. T h e g r e a t e r t h e c o n t r a s t in t h e transparency, the greater will be the c o n t r a s t in the finished print, the action of d a y l i g h t b e i n g to decompose t h e azo derivative, and so prevent r e a c t i o n w i t h t h e " d e v e l o p e r s , " so-called, to be afterwards a p p l i e d ; b u t if we take a piece of t h e sensitive material t h a t has n o t been exposed to light, a n d apply one or more of t h e developers, or, as a dyer w o u l d call i t , a " m o r d a n t , " we at once develop t h e full t i n t or color by the action of t h a t p a r t i c u l a r solution used. T h i s I will now illustrate. [email protected] h a v e here a piece of porcelain coated with a solution of g e l a t i n e and primuline, a n d sensitized in the same b a t h as the c o t t o n cloth. I now paint over one-fifth of its surface, c o n s e c u t i v e l y , with e a c h ' o f the following five solutions or developers: No. I, as y o u see, develops a red color. No. 2 produces a yellow. No. 3 p r o d u c e s an o r a n g e . No. 4 produces a purple. No. 5 produces a dark b r o w n or black. I t o n l y r e m a i n s to well rinse this in water, w h e n the colors will be f o u n d fixed a n d p e r m a n e n t . T h i s demonstra-
486
[I. F. 1.,
Ctzemzca! 5ectwn.
t i o n w i l l i l l u s t r a t e t h e p o s s i b i l i t y of p r o d u c i n g t h e s e v e r a l c o l o r s on o n e a n d t h e s a m e p i c t u r e , as f o l l o w s : Mix a p o r t i o n of e a c h d e v e l o p e r w i t h a t h i n s t a r c h p a s t e , and, w i t h a c a m e l ' s - h a i r p e n c i l , p a i n t o v e r t h e p a r t s w a n t e d of a p a r t i c u l a r color, w i t h t h e p a r t i c u l a r s o l u t i o n i n t e n d e d to s u p p l y t h a t color, of c o u r s e in a w e a k l i g h t , as t h e i m a g e is faintly visible after exposure under the transparency. T h e c o m p o s i t i o n of t h e five d e v e l o p e r s j u s t u s e d is as f o l l o w s - - a n d it is o n l y r i g h t to s a y h e r e t h a t I a m i n d e b t e d f o r t h e f o r m u l v e of t h e s e s o l u t i o n s t o t w o p h o t o g r a p h i c j o u r n a l s , Tile B r i t i s h . / o u r n a / o f P l w t o g r a p f t y a n d A n t l w n y ' s Photograp/zic B u l l e t i n ."
DF.VF.LOVV:I~S. A'o. s--ld,'d. Betanaphthol . . . . . . . . . . . . . . . . . . . . ' Caustic soda, . . . . . . . . . . . . . . . . . . . Water, . . . . . . . . . . . . . . . . . . . . . .
3 ° grains. 4o grains. IO ounces.
2Vo. m-- YeLlow, C r y s t a l l i z e d carbolic acid . . . . . . . . . . . . . . Water, . . . . . . . . . . . . . . . . . . . . . .
5o grains.
Resorcin Water, . . . Caustic soda,
3o g r a i n s .
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. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Io ounces.
Io ounces. 45 grains.
AS, ,/--Pu@le
Naphthylamin . . . . . . . . . . . . . . . . . . . Water, Oxalic acid, .
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.
.
.
. . . . . . . . . . . . . .
.
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.
.
.
.
.
:Eikonogen . . . . . . . . . . . . . . . . . . . . . W~ter, . . . . . . . . . . . . . . . . . . . . . .
60 io
grains. ounces. 6 grains.
~o grains. 1o ounces.
~l'ransparencies on glass, and positives on ceUuloid and o p a l , c a n b e p r o d u c e d as s h o w n b y t h e s p e c i m e n s I h a v e h e r e , a n d w h i c h c a n b e i n s p e c t e d a t t h e c l o s e of t h e meeting. T h e c o m p o s i t i o n of t h e c o a t i n g is as f o l l o w s : Water (distilled) . . . . . . . . . . . . . . . . . . Gelatine, . . . . . . . . . . . . . . . . . . . . . Primuline . . . . . . . . . . . . . . . . . . . . . C h r o m e alum, . .................
2o
ounces. t ounce. 8~, g r a i n s .
2 grains.
June, ~89I.]
C'/eemica! Sectio,z.
48 7
P u t the gelatine to soak in six ounces of water,dissolve t h e primuline in t w e l v e ounces of h o t distilled water, and w h e n dissolved add the g e l a t i n e and the chrome a l u m - - d i s s o l v e d in the r e m a i n i n g t w o ounces of w a t e r - - f i l t e r t h r o u g h cotton, and flow while w a r m on t h e glass or porcelain. When dry immerse for t w o m i n u t e s in the sensitizing solution, w a s h for five m i n u t e s and allow to dry in t h e dark. T h e operation of p r i n t i n g and d e v e l o p i n g is the s a m e as for prints, or cotton, etc.
Chemical Section.
U. F. I.,
tion of lithium fluoride in a q u e o u s solution is a b o u t four calories less than the value which is d e d u c e d from Petersen's e x p e r i m e n t s on neutralization. T h e v a r i a t i o n s in the case of t h e o t h e r fluorides in the a b o v e table are so small that we m a y conclude that w e k n o w their true h e a t of formation w i t h i n the limits of e x p e r i m e n t a l error. T~E
D I A Z ( ) T Y P E P R O C E S S oF P H O T O G R A P H I C D Y E I N G AND P R I N T I N G . BY JOHN CARBUTT.
[Communicated to tke Ckemlca] Section, A1)ri! 2z, IS9z. ]
T h e s u b j e c t I have the p l e a s u r e to b r i n g before the Section this e v e n i n g is t h e " D i a z o t y p e P r o c e s s of Photographic D y e i n g a n d Printing," the d i s c o v e r y of Mr. Arthur G. Green, of London. It is a n e w m e t h o d of producing designs in fast colors on cotton, linen, silk, paper, etc., either from' hand-drawn designs on a t r a n s p a r e n t or semi-transp a r e n t medium, or b y u s e of a p h o t o g r a p h i c transparency. I t was first m a d e public at a m e e t i n g of the British Association for t h e A d v a n c e m e n t of Science, held at Leeds last September. I t is distinctly a positive process ; that is, it yields a positive from a positive. T h e o p e r a t i o n s are five in number, viz : dyeing, sensitizing, printing, d e v e l o p i n g and washing, corresponding v e r y closely in n u m b e r of o p e r a t i o n s required in preparing and p r i n t i n g on p a p e r b y the direct silver process of p h o t o g r a p h i c printing. P r i m u l i n e is t h e base of the new " d i a z o t y p e , " a n d is a l r e a d y in e x t e n s i v e use for dyeing calico in v a r i o u s tints: .Dyeing.--The first operation, then, is to dye our material with "primuline." T o do this t a k e ioo grains of "primuline," add to it t w e n t y o u n c e s of distilled w a t e r b r o u g h t to a boil in a flask over a B u n s e n b u r n e r ; w h e n d i s s o l v e d , pour into a porcelain dish, and i m m e r s e t h e fabric, cotton cloth (the cotton m u s t be free from dressing), or silk, and as soon as t h e piec, es seem t h o r o u g h l y i m p r e g n a t e d with the dye.
June, I89I. ]
Chemzcal Section.
485
remove and rinse in plain water, and squeeze as dry as possible, or place b e t w e e n sheets of b l o t t i n g paper. T h e fabric so p r e p a r e d h a s a p r i m r o s e hue, a n d so far is insensitive to light. 5"ensiti~zing. T h e second operation, or sensitizing, is accomplished b y i m m e r s i n g the dyed fabric in a solution formed of s o d i u m n i t r a t e sixty grains, cold w a t e r thirtytwo ounces, oxalic acid ~oo grains, previously dissolved in two ounces of water. E a c h piece is i m m e r s e d separately and soaked for two or three m i n u t e s , it is t h e n rinsed in water and dried. T h e color of the fabric s h o u l d be of a reddish-yellow hue, and is sensitive to l i g h t ; the operation should be p e r f o r m e d in a weak light, a n d the pieces dried in the dark. Pri~tting. Place in a p r i n t i n g f r a m e a glass transparency, and place over it a diazotized fabric in contact, and expose to d a y l i g h t t e n to t w e n t y m i n u t e s , or s u n l i g h t four to seven minutes. T h e g r e a t e r t h e c o n t r a s t in t h e transparency, the greater will be the c o n t r a s t in the finished print, the action of d a y l i g h t b e i n g to decompose t h e azo derivative, and so prevent r e a c t i o n w i t h t h e " d e v e l o p e r s , " so-called, to be afterwards a p p l i e d ; b u t if we take a piece of t h e sensitive material t h a t has n o t been exposed to light, a n d apply one or more of t h e developers, or, as a dyer w o u l d call i t , a " m o r d a n t , " we at once develop t h e full t i n t or color by the action of t h a t p a r t i c u l a r solution used. T h i s I will now illustrate. [email protected] h a v e here a piece of porcelain coated with a solution of g e l a t i n e and primuline, a n d sensitized in the same b a t h as the c o t t o n cloth. I now paint over one-fifth of its surface, c o n s e c u t i v e l y , with e a c h ' o f the following five solutions or developers: No. I, as y o u see, develops a red color. No. 2 produces a yellow. No. 3 p r o d u c e s an o r a n g e . No. 4 produces a purple. No. 5 produces a dark b r o w n or black. I t o n l y r e m a i n s to well rinse this in water, w h e n the colors will be f o u n d fixed a n d p e r m a n e n t . T h i s demonstra-
486
[I. F. 1.,
Ctzemzca! 5ectwn.
t i o n w i l l i l l u s t r a t e t h e p o s s i b i l i t y of p r o d u c i n g t h e s e v e r a l c o l o r s on o n e a n d t h e s a m e p i c t u r e , as f o l l o w s : Mix a p o r t i o n of e a c h d e v e l o p e r w i t h a t h i n s t a r c h p a s t e , and, w i t h a c a m e l ' s - h a i r p e n c i l , p a i n t o v e r t h e p a r t s w a n t e d of a p a r t i c u l a r color, w i t h t h e p a r t i c u l a r s o l u t i o n i n t e n d e d to s u p p l y t h a t color, of c o u r s e in a w e a k l i g h t , as t h e i m a g e is faintly visible after exposure under the transparency. T h e c o m p o s i t i o n of t h e five d e v e l o p e r s j u s t u s e d is as f o l l o w s - - a n d it is o n l y r i g h t to s a y h e r e t h a t I a m i n d e b t e d f o r t h e f o r m u l v e of t h e s e s o l u t i o n s t o t w o p h o t o g r a p h i c j o u r n a l s , Tile B r i t i s h . / o u r n a / o f P l w t o g r a p f t y a n d A n t l w n y ' s Photograp/zic B u l l e t i n ."
DF.VF.LOVV:I~S. A'o. s--ld,'d. Betanaphthol . . . . . . . . . . . . . . . . . . . . ' Caustic soda, . . . . . . . . . . . . . . . . . . . Water, . . . . . . . . . . . . . . . . . . . . . .
3 ° grains. 4o grains. IO ounces.
2Vo. m-- YeLlow, C r y s t a l l i z e d carbolic acid . . . . . . . . . . . . . . Water, . . . . . . . . . . . . . . . . . . . . . .
5o grains.
Resorcin Water, . . . Caustic soda,
3o g r a i n s .
.
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.
.
.
.
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. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Io ounces.
Io ounces. 45 grains.
AS, ,/--Pu@le
Naphthylamin . . . . . . . . . . . . . . . . . . . Water, Oxalic acid, .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
:Eikonogen . . . . . . . . . . . . . . . . . . . . . W~ter, . . . . . . . . . . . . . . . . . . . . . .
60 io
grains. ounces. 6 grains.
~o grains. 1o ounces.
~l'ransparencies on glass, and positives on ceUuloid and o p a l , c a n b e p r o d u c e d as s h o w n b y t h e s p e c i m e n s I h a v e h e r e , a n d w h i c h c a n b e i n s p e c t e d a t t h e c l o s e of t h e meeting. T h e c o m p o s i t i o n of t h e c o a t i n g is as f o l l o w s : Water (distilled) . . . . . . . . . . . . . . . . . . Gelatine, . . . . . . . . . . . . . . . . . . . . . Primuline . . . . . . . . . . . . . . . . . . . . . C h r o m e alum, . .................
2o
ounces. t ounce. 8~, g r a i n s .
2 grains.
June, ~89I.]
C'/eemica! Sectio,z.
48 7
P u t the gelatine to soak in six ounces of water,dissolve t h e primuline in t w e l v e ounces of h o t distilled water, and w h e n dissolved add the g e l a t i n e and the chrome a l u m - - d i s s o l v e d in the r e m a i n i n g t w o ounces of w a t e r - - f i l t e r t h r o u g h cotton, and flow while w a r m on t h e glass or porcelain. When dry immerse for t w o m i n u t e s in the sensitizing solution, w a s h for five m i n u t e s and allow to dry in t h e dark. T h e operation of p r i n t i n g and d e v e l o p i n g is the s a m e as for prints, or cotton, etc.