4441 4445.output

* GB784848 (A)
Description: GB784848 (A) ? 1957-10-16
Improvements in or relating to fused electrical plugs or adaptors
Description of GB784848 (A)
PATENT SPECIFICATION
Inventor: RONALD FIREDERICK LOEBL 784,948 Date of application and
filing Complete Specification: Feb 7, 1956.
% | No 15916/57.
(Divided out of No 784,847).
Complete Specification Published: Oct 16, 1957.
Index at acceptance: -Class 38 ( 1), E 3 (A 4 A: B 4 A: D 8), E 24.
International Classificatlion:-HO 2 f.
COMPLETE SPECIFICATION
Improvements in or relating to Fused Electrical Plugs or Adaptors We,
LOBLITE LIMITED, a Body Corporate organised under the laws of Great
Britain, of Third Avenue, Team Valley, Gateshead-onTyne 11, do hereby
declare the invention, for which we pray that a patent may be granted
to us, and the method by which it is to be performed, to be
particularly described in and by the following statement: -
This invention relates to fused electrical plugs and adaptors of the
kind in which a fuse of the cartridge type is housed within a recess
in the device and is insertable and replaceable by the release of a
pin without dismantling of the body of the plug or adaptor.
The object of the invention is to provide an improved construction of
retaining means for such a releasable pin.
According to the present invention, in a fused electrical plug or
adaptor of the kind including a housing of insulating material and a
contact pin removably inserted in said housing and serving to retain a
fuse in circuit with the pin in a recess in the housing, the pin is
provided with a radial abutment and a locking member radial to the pin
is movably seated in the housing to engage with the abutment and
retain the pin releasably in the housing.
Preferably spring-loading is provided between the fuse and a contact
in the housng.

The radial locking member may be a grubscrew threaded into a bore in
the housing.
In a convenient construction, the radial abutment consists of a
frusto-conical portion having at its narrower end a radial wall of
greater diameter, the radial locking member being arranged to engage
intermediately along the frusto-conical portion.
In order that the nature of the invention may be readily ascertained,
an embodiment of fused electrical plug in accordance therewith is
hereinafter particularly described with reference to the accompanying
drawing which is an elevation partly in section.
In the drawing there is illustrated a side elevation of a three pin
plug, the other smaller current-carrying pin remote from the viewer
not being visible because it is positioned directly behind the nearer
current 50 pin 1.
The larger earthing pin 2 consists in wellknown manner of a rod
provided with a connection terminal (not shown) at its upper end
within the two-part housing 3 of insulating 55 material.
Within the housing 3 is disposed a terminal 4 mounted at the top end
of a fuseholding recess 5 and having a contact element 6 extending
into the upper end of the 60 recess to contact the upper end of
cartridge fuse 7 At the lower end of the recess there is disposed the
contact pin 1 the upper end of which has a frusto-conical portion 8
adjoining a radial wall 9 In the lower part of 65 the housing 3 there
is a threaded bore in which is threaded a grub-screw 10 which abuts
against the frusto-conical portion 8 of the pin 1 and permits
tightening of the latter in position Where the pin 1 is a flat pin 70
instead of round as shown, the construction of frusto-conical portion
8 and radial wall 9 would be the same, permitting the pin as a whole
to be rotated until the flat blade portion was in correct alignment,
whereafter the 75 grub screw 10 would be tightened to retain the pin
correctly positioned.
The upper end of the pin 1 carries a compression spring 11 which
serves to abut against the lower end of the cartridge fuse 7 80 and
press the latter firnly into contact with the contact element 6 The
other current carrying pin (not shown) could have either a simple
straight-through circuit, or a fused circuit as represented by the
assembly 4-11 85
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* GB784849 (A)
Description: GB784849 (A) ? 1957-10-16
Improvements in electrical measuring instruments
784,849 Date of fling Complete Specification: Oct 2, 1952.
Application Date: July 2, 1951 No 15702/51.
Index at Acceptance:-Classes 35, Al E 1; and 37, I( 5 C 3 5 X: 9: 13
A: 13 C: 13 F 13 T).
International Classification:-G Olr H 02 k.
COMPLETE SPECIFICATION.
Improvements in Electrical Measuring Instruments.
SPECIFICATION NO 784,849
INVETORP: EDWARD JOHN RIORDAN By a direction given under Section 17 (
1) of the Patents Act 1949 this application proceeded in the name of
Aron Electricity leter Limited, a Britlsh company, of 72-82, Salusbury
Road, Kilburn, London, N W 6.
THE PATENT OFFICE, 28th October, 1957 DB 00043/1 ( 9)/3589 100 10/57 R
terial having a high electrical conductivity in close proximity to the
rotatable magnet, a control magnet or a zeroising magnet being fixedly
mounted in an adjusted position so that it may react magnetically with
the rotatable magnet, and a magnetic shield or screen being provided
to afford a return path for the magnetic fluxes produced within the
instrument while at the same time reducing to a minimum the action of
external magnetic fields upon the instrument Such instruments may be
"deflectional", to indicate volts, amperes and so on, and then have
only one set of deflection coils, the control magnet being of an
accurately predetermined strength and being precisely adjusted to its
operating position Alternatively such instruments may be "ratio
meters" and then have two sets of coils set at rightangles to each
other, the zeroising magnet being so positioned and of such a strength
as just to be capable of returning lPrice turn positioned by said

means.
With advantage, the stationary part referred to is a non-magnetic
sleeve adapted to fit within the magnetic shield or screen of the
instrument but it may, alternatively, be this shield or screen itself
Preferably, the magnetic shield or screen is arranged to constitute
the main support and framework for the moving magnet, damping chamber,
coils, bearings and pointer movement.
In order that the invention may be clearly understood, one example of
an instrument functioning as a ratio meter and embodying both the
foregoing and other features of the invention will now be described in
greater detail, with reference to the accompanying drawings in
which:Fig 1 is an elevational view of the spindle, moving magnet and
damping chamber assembly; Fig 2 is a plan view of Fig 1; Fig 3 is a
view similar to Fig 1 showing PATENT SPECIElCATION 784,849 Date of
filing Complete Specification: Oct 2, 1952.
Application Date: July 2, 1951 No 15702/51.
Index at Acceptance:-Classes 35, Al E 1; and 37, I( 503: 5 CX: 9:13
A:130:13 F: 15 T).
International Classification:-G Oir H 02 k.
Improvements in Electrical Measuring Instruments.
We, ARON ELECTRICITY METER LIMITED, a Company registered under the
laws of Great Britain, and EDWARD Jo HN RIORDAN, a Subject of the
Queen of Great Britain, both S of 72 A Salusbury Road, Kilburn,
London, N.W 6, do hereby declare the invention, for which we pray that
a patent may be granted to us, and the method by which it is to be
performed, to be particularly described in and by the following
statement:-
This invention relates to electrical measuring instruments of the kind
(referred to herein as "the kind specified") comprising a small
permanent magnet rotatably mounted within a coil or coils to which the
electrical quantity to be measured is supplied and operatively
connected through motionincreasing gearing to an indicating pointer
that moves over a suitably graduated dial, the instrument being damped
electro-magnetically by disposing a non-magnetic material having a
high electrical conductivity in close proximity to the rotatable
magnet, a control magnet or a zeroising magnet being fixedly mounted
in an adjusted position so that it may react magnetically with the
rotatable magnet, and a magnetic shield or screen being provided to
afford a return path for the magnetic fluxes produced within the
instrument while at the same time reducing to a minimum the action of
external magnetic fields upon the instrument Such instruments may be
"deflectional", to indicate volts, amperes and so on, and then have

only one set of deflection coils, the control magnet being of an
accurately predetermined strength and being precisely adjusted to its
operating position Alternatively such instruments may be "ratio
meters" and then have two sets of coils set at rightangles to each
other, the zeroising magnet being so positioned and of such a strength
as just to be capable of returning lPrice the rotatable magnet to its
zero setting after it has been deflected.
The present invention has for its object to provide improvements in
the construction and manufacture of moving magnet instruments of the
kind specified whereby instruments having improved properties of
reliability and stability may be satisfactorily produced by normal
manufacturing processes under conditions of large scale production.
According to the invention, the non-magnetic material of high
electrical conductivity which is employed for ramping the movements of
the rotatable magnet is formed into a substantially closed chamber
which encloses the magnet and is provided with means adapted to
co-operate with another stationary part of the instrument in precisely
locating the chamber with relation thereto, the chamber constituting
the support for the coil or coils of the instrument which are in turn
positioned by said means.
With advantage, the stationary part referred to is a non-magnetic
sleeve adapted to fit within the magnetic shield or screen of the
instrument but it may, alternatively, be this shield or screen itself
Preferably, the magnetic shield or screen is arranged to constitute
the main support and framework for the moving magnet, damping chamber,
coils, bearings and pointer movement.
In order that the invention may be clearly understood, one example of
an instrument functioning as a ratio meter and embodying both the
foregoing and other features of the invention will now be described in
greater detail, with reference to the accompanying drawings in
which:Fig 1 is an elevational view of the spindle, moving magnet and
damping chamber assembly, Fig 2 is a plan view of Fig 1; Fig 3 is a
view similar to Fig 1 showing 784,849 the deflecting coils and ratio
coils in position, Fig 4 is a plan view of Fig 3; Fig 5 is an
elevational view showing the assembly of Fig 3 mounted within a
nonmagnetic sleeve; Fig 6 is a plan view of Fig 5; Fig 7 is a part
sectional part elevational view of the assembly of Fig 5 mounted in a
magnetic shield, Fig 8 is an elevational view of the assembly of Fig 7
attached to a dial plate; Fig 9 is a fragmentary plan view of Fig.
1.5 Fig 10 is a section of the assembled instrument taken through the
axis of the spindle; Fig 11 is a plan view of Fig 10 with the dial
plate removed; and Fig 12 is a section taken through the cover of the
lower end of the assembly to show the control magnet, adjusting means
therefor and the magnetic shunt.

The example chosen comprises a permanent magnet 1 (Figs 2 & 10) of bar
form mounted at its centre on a spindle 2 having its axis disposed
normal to the wider faces of the magnet 1 At each end the spindle is
provided with a separately produced hardened conical instrument pivot
3 which may be replaced readily should it become worn while in
service.
Surrounding the magnet 1 is an electromagnetic damping chamber
indicated generally at 4 composed of a high conductivity metal such as
copper, this chamber enclosing the magnet 1 with the minimum of
clearance The chamber 4 has a circular base 5 with an upstanding
peripheral wall 6 and a circular cap 7 formed with four radially
projecting arms 7 a equi-angularly spaced around the axis of the
chamber and each formed with a tapered projecting positioning tongue 7
b The base 5 and cap 7 are each formed with a central aperture 8 (Fig
10) through which the spindle 2 may pass with ample clearance, and a
tube 9 of copper or other high conductivity metal is soldered to each
part 5 and 7 to constitute an enclosure for the major portion of the
corresponding projecting part of the spindle 2 The cap 7 is soldered
to the base 5 after the assembly of the parts so that there is a
complete electrical circuit for the eddy currents which are produced
by the movement of the magnet 1 relative to the damping chamber 4 The
latter also constitutes a protective housing and helps to exclude
ferrous or other particles which might otherw O wise interfere with
the free movement of the magnet 1 It should be noted that the external
diameter of the tubes 9 surrounding the spindle ends is not greater
than the width of the arms 7 a projecting from the cap 7 of 3 the
damping chamber 4.
Upon the one end of the spindle 2 (referred to herein as the "top" or
"upper" end, for reasons of simplicity only) there is secured a
toothed quadrant 10 carrying balance weights 11, the quadrant 10
having 70 teeth 12 over a circumferential length that subtends an
angle of somewhat more than ' at the axis of the spindle 2 This
quadrant 10 is secured in a predetermined angular relationship to the
permanent 73 magnet 1, so that the axis of the latter is at
right-angles to the plane bisecting the angle subtended by the toothed
periphery of the quadrant 10.
The coils 13 and 14 (Figs 3, 4 and 10) for SO the instrument are
separately wound to the appropriate configuration and cemented in any
usual manner so that they are self-supporting, i e require no former
as such The deflecting coils 13 are adapted to fit tightly 85 upon the
damping chamber 4 one at each side of the tubular projections 9
therefrom, these coils 13 bearing against the opposite edges of two
diametrically opposed arms 7 a of the cap 7 of the chamber 4 The ratio
90 coils 14 are then fitted tightly over the deflecting coils 13, at

right-angles to the same.
so that they bear against the opposite edges of the remaining pair of
diametrically opposed arms 7 a of the cap 7 The posi 95 tioning
tongues 7 b on the four arms 7 are then the only portions of the
damping chamber 4 which extend outside the coil assembly except for
the ends of the tubes 9 surrounding the spindle 2 of the magnet 1 M A
longitudinally split sleeve 15 (Figs 5, 6 and 10) of a non-magnetic
material such as copper is produced by making an appropriate stamping
from sheet material and rolling it to cylindrical form This sleeve 15
is 105 arranged to exhibit inwardly projecting ribs 16 (of channel
shape when seen from the exterior) that extend longitudinally of the
sleeve 15 Each rib 16 starts from a rectangular notch 17 formed from
the lower edge to O of the sleeve 15, there being four such notches
equi-angularly spaced around the axis of the sleeve 15 At the
appropriate points along the length of the ribs there are formed
apertures 18 of such a size that, when the sleeve 113 is applied
around the assembly of damping chamber 4 and coils 13 and 14, the
positioning tongues 7 b on the arms 7 of the chamber 4 will fit
tightly in the apertures 18 to position the assembly in relation to
the 120 sleeve 15, which latter closely embraces the coils 13 and 14
Two diametrically opposed slots 19 are formed through the sleeve 15,
each slot 19 being located a short distance from the lower edge of the
sleeve 15 and 12 l midway between two of the notches 17.
A screen plate 20 of a material having a low magnetic retentivity, e g
a nickel-iron alloy such as that known under the Registered Trade Mark
"Mumetal", is fitted over 130 correctly positioned in the notches 17
and 25, they are held firmly in place by an end cover 32 (Figs 7, 8,
10 and 12) which is secured in position by means of screws 33 engaging
screw-threaded apertures 34 formed 70 in the flat clamping bar 27 to
which reference has been made above.
This end cover 32 is formed from a material of low magnetic
retentivity and is circular in shape Centrally it carries a rotatable
75 bush 35 upon the upper end of which is secured a zeroising member
in the form of a permanent bar magnet 36 that may be adjusted
angularly to a small extent about the axis of the bush 35 by means of
an eccentric 80 or cam device 37 This device 37 is a disc mounted
eccentrically on a screw 38 which extends through the end cover 32 and
is operable from the underside thereof The disc 37 is received between
the legs 39 of a 85 thin U-shaped member 40, the base of which is
considerably wider than the legs 39 and is secured to the bush 35
below the magnet 36 such that movement of the member 40 caused by
rotation of the disc 37 will cause 90 the bush 35 to rotate and adjust
the angular position of the zeroising magnet 36 relative to the axis
of the spindle 2 An adjustable magnetic shunt 41 is secured to one end

of a grub-screw 42 which threadedly engages a 95 threaded sleeve 43
which passes through the cover 32 such that rotation of the screw 42
will raise or lower the shunt 41 to enable shunting of the magnetic
flux between a pole or poles of the zeroising magnet 36 and the 100
screen 24 to be controlled when the end cover 32 is secured in place A
V-bearing 44 for the lower end of the spindle 2 is mounted within a
hollow grub screw 45 which threadedly engages a thread formed 105
co-axially through the bush 35 such that the axial position of the
V-bearing 44 can be adjusted by rotation of the grub screw 45.
As stated above, the end cover 32 is secured in position over the
lower end of the screen 110 24 by screws 33 passed through the cover
32 into the clamping bar 27 which has previously been inserted through
the aligned slots 19 and 26 in the sleeve 15 and screen 24
respectively, the tightening of these screws 115 33 drawing the bar 27
down to the lower ends of the slots 19 and 26 and securely clamping
the sleeve 15 in relation to the screen 24 It will be noted that all
the parts thus far described are now firmly secured 120 together and
correctly and precisely positioned in relation to each other.
A V-bearing 46 for the upper end of the spindle 2 is mounted within a
hollow grub screw 47 which threadedly engages the 125 centre of a
cruciform member 48 (Fig 11) such that rotation of the screw 47 will
adjust the axial position of the bearing 46 The cruciform member 48 is
preferably a die casting in light alloy, having four arms 48 a 1230
the upper end of the chamber-and-coil assembly beneath the toothed
sector 10 tonether with a washer 20 a, the two being carried on the
upper end of the tube 9 which end is suitably reduced in diameter to
provide a shoulder 9 a to support the washer 20 a and screen plate 20
This plate 20, which is generally circular in shape and is slotted
radially as at 21 (Fig 6) to permit the passage of the plate over the
spindle 2, is secured in position by engaging tongues 22 thereon in
apertures 23 formed at the upper ends of the ribs 16 in the
non-magnetic sleeve 15, the washer 20 a being slotted radially as at
1.5 20 b to permit the tongues 22 to pass therethrough Only these
tongues 22 are provided on the plate 20 spaced 90 ' apart, the fourth
tongue being omitted.
There is now available a subsassembly '0 comprising the magnet 1,
spindle 2, damping chamber 4, coils 13 and 14, toothed sector 10,
non-magnetic sleeve 15, and top screen plate 20, and this is inserted
axially into a screen or shield 24 in the form of a longitudinally
split cylinder of a material having a low magnetic retentivity This
screen 24 is stamped from sheet material, with all the necessary slots
and apertures already formed, before being bent to the cylindrical
shape.
(o Among these slots and apertures are four notches 25 formed from the

lower edge of the screen and equi-angularly spaced around the axis of
the latter, and also two diametrically opposed slots 26 located at a
short dis, tance from the lower edge, each midway between two of the
notches 25 Similarly disposed slots 19 having been formed in the
non-magnetic sleeve 15 during its production, it is possible to insert
a flat clamping bar 27 through the several slots 19 and 26 when the
sub-assembly is correctly positioned inside the screen 24.
The leads 28 from the coils 13 and 14 of the sub-assembly are provided
with anchor4,5 ing means which are adapted to engage in the notches 17
and 25 in the sleeve 15 and screen 24 respectively and, while
assisting in the positioning of these parts relative to each other,
also relieve the coils 13 and 14 of pulls and stresses which may be
applied to the outer ends of the leads 28 These anchoring means each
comprise a grommet 29 of insulating material which is moulded around
the leads 28 from a coil 13 or 14 at a location where these leads 28
have first each been twisted about a common thread of a similar
insulating material Suitable materials are, mouldable thermoplastic
compositions such as polyvinyl chloride.
Each grommet 29 is shaped so that its inner end will be a close fit in
the corresponding notch 17 in the non-magnetic sleeve 15 and its outer
end is grooved as at 31 (Figs 5 and 7) to fit in the respective notch
25 in the -G 5 screen When the grommets 29 have been 3 784,849 which
are each adapted to fit closely in the corresponding one of a series
of four notches 49 formed in the screen 24 to extend from the upper
edge thereof One of these arms is formed with an integral extension 48
b that projects outside the screen to termiinate in a bifurcated
bracket of which the arms 50 are spaced apart by a short rod 51
parallel to the axis of the spindle 2 and extend substantially
tangentially with respect to the curved surface of the screen 24, both
the screen 24 and the sleeve 15 being cut away as at 52 and 52 a
respectively to accommodate the bracket It is for this reason that i 5
the screen plate 20 has only three tongues 22 the space 22 a which
replaces the fourth tongue being arranged to lie opposite these
cut-away portions 52 and 52 a The free extremities of the arms 50 each
carry a hollow grub screw 54 containing an axially adjustable
V-bearing 53 for the appropriate end of a short spindle 55 disposed
parallel with the main spindle 2 and provided with detachable hardened
conical pivots 56 Between its ends, the short spindle 55 has secured
thereon a toothed pinion 57 adapted to mesh with the quadrant gear 10
on the main spindle 2 and the shank 58 of an indicating pointer 58, 60
with its appropriate balance weight 59 The pointer proper is a needle
60 attached to the shank 58 by any suitable means such as a clip 58 a
and an adhesive The shank 58 is suitably cranked so that the operative
end 60 is located in a plane spaced upwards from the upper face of the

cruciform die casting 48.
The securing of the cruciform die casting 48 to the screen 24 is
effected with the aid of a flat or strip spring 61 In the screen 24
are two diametrically opposed slots 62 (Figs.
7 and 8) which are wide enough at the lower ends to admit the widest
part of the flat spring 61 but are only wide enough at the upper ends
to receive as a close fit a narrow tab-like end 63 of the spring 61
The length of the spring 61 is such that when the tablike ends 63
thereof are engaged in the narrower ends of the slots 62 they also
project radially outwards from the screen 24 to a sufficient extent to
receive fixing screws 63 a (Figs 8 and 9) which pass through holes 64
formed one in each end 63 of the spring 61 The tab-like ends 63 meet
the body of the spring 61 at shoulders 65 which bed snugly against the
inner surface of the screen 24 and the arrangement is such that the
spring 61 is then under tension and applies a downward pressure to the
cruciform die casting 48 The spring 61 has a central aperO ture 66 to
give access to the adjusting grub screw 47 of the bearing 46 for the
upper end of the main spindle 2.
A circular dial plate 67 (Figs 8, 9 and 10) with which the operative
end 60 of the pointer is adapted to co-operate is secured to the unit
assembled in the manner described above This may be effected
conveniently by engaging the fixing screws 63 a received in the
tab-like ends 63 of the flat spring 61 with screw threaded apertures
63 b;'1 formed in the dial plates 67 The dial plate 67 is dished as at
68 and the dished portion is formed with a pair of slots 69 (Figs 8
and 9) into which a pair of upstanding lugs formed on the screen 24
are adapted to 7 o fit The dial plate 67 has a central aperture 71
through which the pointer extends to co-operate with appropriate
markings formed on the outer peripheral portion of a calibrated
annular scale 72 which is secured S(o to the base of the dished
portion by means of a pair of diametrically opposed screws 73 of which
one is shown in Fig 10 An aperture 75 (Fig 9) is formed through the
dial plate 67 to overlie the adjusting screw 47 s 5 of the upper
V-bearing 46 to provide free access thereto for adjustment purposes It
will be appreciated that the unit or instrument movement is carried
entirely from the dial plate 67 The range of movement of O' the
pointer 60 may be 270 for an angular movement of the rotatable magnet
1 of 90 '.
An instrument constructed in the foregoing manner may have its parts
produced by normal manufacturing operations and q 5 they may be
assembled accurately and rapidly by operators having the degree of
skill usually found among those employed on the mass-production of
electrical measuring instruments l HY It will be appreciated that the
instrument described above may be used to measure the ratio of two

electrical quantities one of which is applied to the deflecting coils
13 and the other of which is applied to the 10.
ratio coils 14, the magnet 1 being deflected in accordance with the
ratio of the quantities being measured.
The instrument may also be used as a "deflection" instrument in which
case the 110 coils 14 are omitted and a control magnet is fitted to
determine the deflection of the moving magnet which will be produced
when an electrical quantity of a given magnitude is supplied to the
deflecting coils 13 The 115 magnet 1 is then deflected in accordance
with the quantity applied to the coil 13, the movement of the magnet 1
being amplified by the quadrant 10 and pinion 57 to move the operative
end 60 of the pointer over the 120 calibrated scale 72 to provide a
direct reading of the magnitude of the quantity being measured.
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* GB784850 (A)
Description: GB784850 (A) ? 1957-10-16
Improvements in or relating to hydraulic control valves
I, KARSTEN ALFRED OVRETVEIT, a Nor-
wegian Subject, of Fjell, Bergen, Norway, do hereby declare the
invention, for which I pray that a patent may be granted to me, and
the method by which it is to be performed, to be particularly
described in and
by the following statement:-
This invention relates to an hydraulic control valve for use in an
hydraulic system (hereinafter termed "the kind referred to")
comprising a constant delivery pump and a motor said valve being

employed for controlling the rate of flow of the fluid to said motor
from said pump and thereby to regulate the functioning of said motor
said valve comprising a port controlling member associated with a main
port or ports for providing communication between the pump and motor
and across which said controlling member is adapted to be moved.
Said valve may comprise a piston operating slidably in a cylinder said
piston having a piston head or heads and said cylinder having a port
or ports which are crossed by said piston head or heads.
Where such motor is employed for driving a winch, for example, the
rate of lifting or lowering has to be controlled and it must be
possible to hold the load suspended and to be able to commence to lift
again from the suspended position without any intermediate drop of the
load as the valve is operated.
It is of course understood that though the quantity per unit of time
delivered by the pump remains substantially constant the quantity
actually passed through the motor varies with the speed of the motor
so that fluid not used in the motor is returned to the pump It is also
well known that where the motor is being used to lift a load, as when
coupled to a winch, in order to hold the load the valve must be
positioned to shut :' 784,850 off the supply from the pump and to
prevent the motor from pumping the fluid back into 45 the return pipe
It is also known that the pressure in the hydraulic system should be
kept as low as possible to avoid unnecessary generation of heat.
In any such hydraulic circuit the complete 50 closure of the control
valve can produce an undesirable rise of pressure in the circuit and
result in damage andlor overheating of the hydraulic fluid.
It is known to provide release valves 55 which have for object to
prevent a dangerous rise in pressure in the hydraulic circuit if the
delivery pipe from the pump is throttled.
It is also known to provide spring-loaded by-pass valves for the same
purpose which 60 by-pass valves are additional to the control valve by
which the flow of liquid to the motor may be regulated.
This invention further relates to hydraulic control valves and more
particularly to 65 control valves for use in hydraulic systems in
which a valve member movable in a housing is adapted to control the
supply of hydraulic liquid to a plurality of motors or an hydraulic
motor or motors with a 70 plurality of chambers.
It is known in hydraulic power transmission systems having a pump
adapted to deliver a constant volume of hydraulic liquid to obtain a
variation of speed of the driven 75 shaft adapted to be driven by a
number of working chambers of a motor or motors adapted to be
connected individually or collectively in any desired combination in
the hydraulic circuit of the said pump the 80 variations in speed and
of mechanical advantage depending on the number of working chambers

drawing liquid from the pump.
A single motor may have a plurality of rotors or working chambers
adapted to be 85 brought into and out of the circuit to proPATENT
SPECIFICATION
Date of filing Complete Specification: March 2, 1953.
Application Date: Sept 3, 1952 No 22190/52.
Index at Acceptance:-C Iaso 69 ( 2), O( 6 E: 6 F:O 1 X).
International Clausification:-F Old.
Improvements in or relating to Hydraulic Control Valves.
784,850 duce a change of speed in a similar manner.
One of the difficulties with such a construction is that the rotor in
the working chamber not connected in the pressure circuit continues to
operate being driven by the other or others in the system and
therefore acts as a pump for the liquid therein This liquid has to be
circulated, as the system would become locked if the liquid were
trapped, and moreover the working chamber must be kept supplied with
liquid so that the air does not enter the circuit The circulation must
be as free as possible so as to avoid the waste of energy by the pro1
l duction of excessive pressure or the danger of the entry of air into
the system if a vacuum is produced One way of effecting this is to
provide a short circuit for the working chamber that is idling Another
problem is to secure a smooth change over from power generation to
idling and it is during this change over that the greatest danger of a
build up of pressure or vacuum exists.
2-5 One of the objects of the present invention is to provide an
improved hydraulic control valve of simple construction which will
overcome some or all of the above disadvantages.
According to the present invention I provide an hydraulic control
valve for use in an hydraulic system of the kind referred to
characterised by the provision of a by-pass channel and auxiliary port
associated with at least one main port and a non-return safety valve
in said by-pass channel adapted to come into operation when said main
port is obstructed.
An hydraulic valve according to one u 11) embodiment of the present
invention comprises a housing provided with a plurality of inlet and
exhaust ports adapted to be connected to a plurality of working
chambers of a motor or associated motors and a single movable valve
member in said housing arranged to connect said inlet ports in
succession to a liquid pressure circuit and to short circuit the inlet
and exhaust ports of those working chambers not connected in the
pressure circuit A non-return valve is provided between said inlet
ports and a source of liquid supply which may be the exhaust circuit

from said working chamber.
Referring to the diagrammatic drawings filed with the Provisional
Specification:-
Fig 1 is a longitudinal section showing diagrammatically one form of
valve made in accordance with the present invention showing only the
general arrangement of the de O ports.
Fig 2 is a fragmentary sectional detailed view of the valve shown in
Fig 1.
Fig 3 is a transverse section of a further modified form of valve made
in accordance with the present invention.
Figs 4 to 8 show diagrammatically the form shown in Fig 3 with the
rotary valve in various positions.
In the form shown in Fig 1 the valve housing 2 is provided with a
pressure inlet 70 port 4 and return port 6 adapted to be connected to
a pump (not shown) of the constant delivery type These ports are
arranged in spaced relation to each other and the distance between
them is approxi 75 mately equal to the distance of each from the
nearest end of the housing Also provided in the wall of the housing 2
are a number of other parts as follows:At the extreme lower end is the
inlet port So adapted to be connected to one of the working chambers
of a multi-rotor motor (not shown) whilst at the upper end are inlet
ports 12, 14 and 16 adapted to be connected to the remaining three
working chambers of 85 the said motor Centrally of the housing 2 are
provided exhaust ports 18 and 20, the exhaust port 18 receiving the
exhaust liquid from the working chambers to which the inlet ports 12,
14 and 16 are connected and 90 likewise the exhaust port 20 receives
the exhaust liquid from the working chamber to which the inlet port 10
is connected.
Disposed in the chamber 2 is a valve member 22, having an upper head
24 and a lower 05 head 26 enclosing with the cylinder a space 27 and a
central bore 28, which opens above and below the heads 24 and 26
respectively.
It will be noted that the inlet port 4 and outlet port 6 are spaced so
that they are 100 spaced closer together than the undersides of the
heads 24 and 26, with the result that the valve member 22 can be moved
to a central position where free flow can take place between the ports
4 and 6 10 a If it is desired to lock the motor or motors against
movement in the forward direction the valve member 22 is moved to the
neutral position with the head 24 above the port 6 and the head 26
below the port 4 When 11, moved into this position from forward drive
no liquid can return from the ports 10, 12, 14 or 16 because of the
heads 24 and 26 and the motor cannot turn in reverse Likewise from
reverse drive as the pump circuit 115 is full no liquid can escape
from the ports 18 and 20 if means are provided to prevent any escape

to the expansion tank normally provided for such an hydraulic system
unless the pressure rises above a predetermined 120 safe maximum.
As will be seen from Fig 2 the channels 12 ', 141 and 161 leading to
the ports 12, 14 and 16 are provided with non-return valves 32, 34 and
36 respectively, so that when the 125 piston head 24 closes or
substantially closes the inlet port, a vacuum is prevented from
occurring in the circuit of any working chamber so shut off (in the
present case the one connected to the inlet port 14), by reason 130
784,850 of the fact that the non-return valve 34 can lift to admit
liquid from the inlet channel 16 ', which is drawn from the liquid
exhausted by the working chamber connected to the inlet port 12 or
from the reservoir or expansion tank for maintaining the system filled
with liquid.
The non-return valve 32 is positioned between the ports 12 and 14 and
the nonreturn valve 34 between the ports 14 and 16.
In the case of the non-return valve 36 this opens into a channel or
duct 38 leading to the port 6.
The ports 12, 14 and 16 may be proportioned relative to the head 24 so
that as the piston head 24 moves across these ports they are never
completely closed, but at the same time the gap is not sufficient to
allow liquid to escape round the head 24 too freely, whereby the
pressure in any of the other inlet ports under pressure, does not fall
below that which is sufficient to sustain the load on the motor
Likewise the port 18 may be proportioned relative to the head 24.
Alternatively as shown in Fig 2 a nonreturn vaive 40 is provided and
positioned between the duct 38 and the port 18 to prevent a vacuum
forming in the working chamber connected to the port 18.
It will be evident that with a control valve made as described above
it is possible to move the valve member from its lowest position, in
which liquid is first admitted to all the working chambers via the
inlet ports 10, 12, 14 and 16, and a creeping motion can be given to
the motor After the full flow has been established to all the working
chambers, changes of speed can be obtained, without any intermediate
drop or noticeable check in the operation, by sliding the valve member
22 to shut off the inlet ports 16 14 and 12 in succession, leaving
open only the inlet port 10, so that all the liquid has to pass
through one working chamber This position of the valve member 22 gives
maximum speed with, of course, minimum mechanical advantage or torque.
To operate in reverse it is only necessary to lower the valve member
22 from the neutral position in which the head 24 is above the port 6
and the head 26 below the port 4 to a position in which the port 6 is
open partly above the head 24 so that motive liquid entering the port
4 passes to the working chambers connected with the ports 18 and 20
When the head 24 is between the ports 6 and 18 the working chambers

connected to the ports 18 and 20 are receiving all the pressure liquid
from the pump If a greater speed in reverse is required all that is
necessary is to position the head 24 between the ports 18 and 20 so
that all the motive liquid has to pass through the workingl chamber
connected to the port 20.
In the form shown in Figs 3 to 8 the same reference numerals have been
used to indicate corresponding parts The valve is of the rotary plug
type and the housing 2 is provided with a pressure inlet port 4 and
return port 6 adapted to be connected to 7,0 a pump (not shown) of the
constant delivery type These ports are arranged almost diametrically
opposite to each other around the periphery of the bore of the housing
2.
Also provided in the wall of the housing 2 75 are a number of other
ports as follows:In one part periphery between the ports 4 and 6 are
the inlet ports 10, 12, 14 and 16, the port 10 being adapted to be
connected to one of the working chambers of a multi 80 rotor motor
(not shown) and the inlet ports 12, 14 and 16 being adapted to be
connected to further working chambers of the said motor Near the port
6 on the other part of the periphery of the housing 2 are pro 85 vided
exhaust ports 18 and 20, the exhaust port 18 receiving the exhaust
liquid from the working chambers to which the inlet ports 12, 14 and
16 are connected and likewise the exhaust port 20 receives the exhaust
90 liquid from the working chamber to which the inlet port 10 is
connected Disposed in the chamber 2 is a valve member 22, carried on a
shaft 23, having heads 24 and 26, the body of the valve member 22
being smaller 95 than the bore of the housing 2 forming communication
channels 28 and 29 respectively.
It will be noted that in one position of the valve member 22 (Fig 3)
free flow can take place between the ports 4 and 6 along the 100
channel 29 It will also be seen that as in the constructions shown in
Figs 1 and 2 the head 24 is narrower than the ports 12, 14, 16 and 18.
As in the modified form shown in Fig, 2 I 05 the ports 12, 14 and 16
are provided with non-return valves 32, 34 and 36 respectively, so
that when the piston head 24 obstructs the inlet port, a vacuum is
prevented from occurring in the circuit of any working 110 chamber so
shut off (in Fig 5 the one connected to the inlet port 14), by reason
of the fact that the non-return valve 34 can lift to admit liquid from
the inlet port 16, which is drawn from the liquid being re 115 turned
to the suction side of the pump or from the reservoir or expansion
tank for maintaining the system filled with liquid.
The non-return valve 32 is positioned between the ports 12 and 14 and
the non 120 return valve 34 between the ports 14 and 16.
In the case of the non-return valve 36 this opens into a channel or
duct 38 leading to the port 6.

As with the form shown in Fig 2 a non 125 return valve 40 is provided
and positioned between the duct 38 and the port 18 to prevent a vacuum
forming in the working chamber connected to the port 18 and a further
non-return valve 42 is positioned 13 ( between the ports 10 and 12
which comes into operation if the valve member 22 is turned too far.
The operation is substantially the same as for the forms already
described Fig 3 shows the valve member 22 in the neutral position with
the rotors locked In Fig 4 all the chambers are being supplied with
pressure fluid from the port 4 via the communication channel 28 In Fig
5 the rotary valve member 22 is in the same relative position as the
piston valve 22 of Figs 1 and 2 Fig 6 shows the valve member 22
crossing the port 12 to move into the position for highest speed when
the head 24 is between the ports 10 and 12 In Fig 7 the valve member
22 is positioned for slow speed reverse and finally in Fig 8 for high
speed reverse.
It will be realised that in certain circumstances it may be desirable
to provide a different arrangement in which the motor is of the
balanced type having a single speed, but two working chambers
oppositely arranged and adapted to work in parallel so that the
pressure on both sides of the rotor is balanced Obviously any number
of chambers could be employed symmetrically disposed around the rotor
to provide a balanced rotor and the invention is not limited to the
use of two In order to provide for speed variation a plurality of
pumps are employed For slow speed the motor is supplied from one pump,
and for each increase in speed an additional pump is brought into
service.
In order to balance the rotary valve shown in Figs 3 to 8 a channel 50
and port 52 are provided In order to correct further for any
difference in pressure due to the area of the valve surface on the
side of the channel 50 being less than the area on the side of the
channel 28 the channel 50 is extended axially in both directions
beyond the axial limits of the ports and the communicating channel 28.
Referring to the drawing filed herewith: Fig 1 is a diagrammatic
sectional elevation of a modified form of control valve 5) made in
accordance with the present invention suitable for use with a two
speed winch motor.
Fig 2 is a diagrammatic sectional elevation of a modified form of
system to that shown in Fig 1 filed herewith, wherein the port 10 has
been moved to another position and the cylinder lengthened.
Fig 3 is a transverse section on the line III-III of Fig 1.
In Fig 1 of the drawing filed herewith the construction illustrated is
substantially similar to that shown in Fig 1 of the drawings filed
with the Provisional Specification but has been modified by the
addition of relief valves 60 and 62 associated with the ports 4 and 6

respectively and additional ports 64 and 66 respectively The purpose
of the valve 60 and port 64 is to relieve any excessive pressure which
might develop in the port 4 on the delivery side of the Th pump as the
head 26 crosses the port 4.
In like manner the valve 62 and port 66 are provided for the purpose
of relieving the vacuum on the suction side of the pump in the port 6
as the head 24 crosses the, port 6.
In like manner an additional port 68 has been provided associated with
the check valve 40 for the purpose of relieving excessive partial
vacuum in the port 18 as the m i head 24 crosses the port 18 to reduce
the risk of the entry of air into the system or the formation of gas
in the circuit Similarly, a further additional port 70 connected by a
passage 72 to a chamber 74 beneath the Shead of the valve 36 relieves
excessive partial vacuum in the port 16 as the piston head 24 crosses
the latter In order to avoid the use of springs for controlling these
valves, 60, 62, 36 and 40 respectively, these have been arranged to be
seated by gravity and the small bleed holes 76 prevent hydraulic
locking of the valves The operation of this valve will be obvious from
the foregoing description p
In certain circumstances it may be desirable to be able to change over
the duties of the motors and pump so that the motors become pumps and
the pump becomes a motor 3 i Turning now to Fig 2 of the drawings
filed herewith this Figure has been added for the purpose of
illustrating how the valve shown in Fig 1 hereof can be modified so as
to make it suitable for use in the case 105where it is desired to
change over the duties of the motor and pump so that the motor
operates the pump and the pump operates the motor respectively With
the construction shown in Fig 2 as will be apparent from 110 the
description which follows no modification is required as the valves
there shown will perform the same function when the duties of the
motors and pumps are interchanged but with the construction shown 115
in Fig 1 of the drawings filed with the Provisional Specification the
interchange could not be effected completely because of the position
chosen for the port 10 which position was chosen for the purpose of
giving 1 _ 1 a more compact construction of the valve and reducing the
stroke In that case the pump now changed to a motor could onlv be
driven in one direction The ports 10, 16, 18 and 20 for the channels
101, 161, 181 125 and 201 are now to be considered as being connected
to the pump and the ports 4 and 6 to the motor It will be seen that
the cylinder has been lengthened in order to provide an increased
travel for the piston 22 130 784,850 Referring now to Fig 3 which
shows diagrammatically a construction wherein the cylinder wall at
each of the port openings is provided with grooves 80 separated by a
land 82 said grooves having the same width as the port with which they

are associated and being therefore wider than the piston head whereby
a pressure around the piston is balanced as the same crosses the port
In order to prevent the piston head falling into the port a dividing
wall 84 is provided across the centre of the port, the inner face of
which is continuous with the cylinder wall To prevent sideways
movement of the piston, similar ribs 86 are provided on each side of
the port opening arranged diametrically of each other with respect to
the distance.
With the arrangement of ports as shown the motor connected to the
ports 4 and 6 can be driven in either direction With the piston shown
in the position illustrated in Fig, 2 both ports 10 and 16 are
delivering pressure fluid to the port 4 of the motor and therefore the
motor is being driven at maximum speed.
If the piston 24 is moved downwards so that oil entering the port 16
can no longer reach the port 4 then the motor would be operating at
low speed Variations of speed are of course obtainable in intermediate
positions.
To slow the motor down still further a continuation of the movement of
the piston 24 across the port 10 will shut off the oil supply from
that port to the port 4 and the motor will be brought to rest.
The neutral position is when the ports 10 and 20 respectively are
between the heads 24 and 26 of the piston In order to obtain reverse a
still further downward movement of the piston 22 is carried out so
that the port 4 and port 20 are connected to provide slow speed
reverse drive When both ports 18 and 20 are connected to the port 4
all the oil from the sump entering the ports 16 and 10 pass through
the motor and back through the ports 18 and 20 thereby providing full
speed in reverse and of course any intermediate speed is obtainable as
heretofore.
It will be appreciated that in Fig 2 above described the relief valves
36, 40, 60 and 62 of Fig 1 hereof have been purposely omitted not only
for the purpose of clarity but because the precise arrangement would
not provide a construction in which the duties of motor and pump are
interchangeable.
If the valves shown in Fig 1 were added to the construction shown in
Fig 2 the motor could only be operated in one direction but it would
provide a construction in which the speed of the motor was varied
according to the number of pump or pump chambers from which it was
supplied.
It will be appreciated that in the construction shown in Fig 2 of the
drawings accompanying the Provisional Specification the parts are
illustrated in the position for high speed drive When 14 is the main
port to be obstructed the by-pass channel 161, valve 34 and channel 14
' and the port 16 becomes the auxiliary port When port 12 is

obstructed then port 14 becomes the auxiliary port the by-pass channel
comprising channel 141, valve 32 and channel 12 '.
When port 16 is obstructed 38, 36 to 161 is the by-pass channel and
port 6 which is connected to ports 18 and 20 becomes the auxiliary
port.
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* 5.8.23.4; 93p
* GB784851 (A)
Description: GB784851 (A) ? 1957-10-16
Improvements in or relating to alkaline electrlc accumulators
A high quality text as facsimile in your desired language may be available
amongst the following family members:
AT181300 (B) BE515722 (A) CH314756 (A) DE899216 (C)
FR1066769 (A) NL88619 (C)
AT181300 (B) BE515722 (A) CH314756 (A) DE899216 (C)
FR1066769 (A) NL88619 (C) less
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The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
-I

Date of Application and Filing Complete Specification: Nov 28, 1952.
784,851 No 30237 t 52, l;)) Application made in Germany on Dec 1,
1951.
Index at Acceptance-Class 53, BD(IOA: 12), BSIA( 3: 5: 6: 7; 10: 14:
X), B 53 A Lo International Classification:-H Olm.
Improvements in or relating to Alkaline Electr Ic Accumulators.
We, ACCUMULATOREN-FAB Ri K AKTIENGESELLSCHAFT, a German Company, of
Dieckstrasse 42, Hagen in Westfalen, Germany, do hereby declare the
invention, for which we pray that a patent may be granted to us, and
the method by which it is to be performed, to be particularly
described in and by the following statement:-
This invention relates to gas-tight alkaline accumulators.
It has been shown by experience that after long use under practical
conditions the individual cells of alkaline accumulator batteries do
not always possess uniform capacity with respect to one another even
when they are provided in manufacture with equal quantities of active
material having the same properties In spite of similar electrical
treatment, the series-arranged individual cells of the battery wear
out in course of time with varying rapidity In the discharge of the
battery the voltage across some elements prematurely drops whilst
others still have sufficient voltage to enable further current to be
taken from the battery Finally, the differences in capacity of the
individual cells-especially with defective servicingcan be so great
that some cells reverse their polarity when the battery is completely
discharged In the further discharge flow of current after this
reversal of polarity, oxygen or hydrogen or both are soon generated at
the electrodes of such elements after the potential thereof has fallen
below zero point and after change of their polarity and according as
to whether the positive or negative electrodes, or both together,
reverse their polarity, such generation of gas corresponding to the
discharge current This generation of gas on the one hand produces a
risk of the battery casing exploding if hydrogen or an explosive
mixture of hydrogen and oxygen is formed, and on the other hand the
elements enclosed in a gas-tight manner in the casing are liable to
swell up and explode owing to the gas formation.
This is also to be feared with elements provided with gas absorbing
electrodes, for example according to British Patent Specificatiin No
433,809, since these electrodes are 50 only able to cope with the
small quantities of gas generated due to charging and fail to function
in the event of reversal of their polarity.
It is an object of this invention to provide 55 a gas-tight alkaline

accumulator in which gas formation does not occur when the accumulator
is discharged beyond the point at which reversal of polarity of the
electrodes occurs 60 This invention provides a gas-tight alkaline
accumulator in which either only the electrode having the smaller
capacity or each electrode contains an additive which, in the event of
a current continuing to flow through 65 the accumulator in the
discharge direction after the polarity of the accumulator has become
reversed, undergoes an electrochemical reaction and thereby suppresses
the evolution of gas from the said electrode 70 or electrodes.
It has been found that the generation of hydrogen which occurs at the
positive electrode (nickel-oxide electrode) immediately after reversal
of polarity may be effectively 75 suppressed by loading this electrode
not only with the normal mass usually employed (nickel hydroxide +
conductive material, for example, graphite or nickel flakes), but also
with an 'anti-polar' mass, that is, in 80 this case, with a cathodic
reducible oxide, for example cadmium oxide or cadmium hydroxide, that
is to say with a material like that previously used in alkaline
accumulators for loading the negative electrode 85 and which is
reducible at a potential value below the separation potential of
hydrogen.
The cadmium oxide present in the positive electrode to a certain
extent acts as an acceptor for hydrogen in that with pole re 90
784,851 -ersal of the element it is reduced at a malerially lower
potential than is necessary for generation of hydrogen at the
electrode It s only after the cadmium oxide present has been reduced
to metal that the electrode can generate hydrogen upon further passage
of current If, moreover, the opposite electrode, i e the negative
electrode of the element is made sufficiently large and efficient, i e
is provided with the necessary excess of negative mass, such element
is unable to generate any gas, either hydrogen or oxygen, at the end
of the discharge with reversal of polarity.
Conversely, according to the invention the capacity of the positive
electrode may be made greater than that of the negative electrode and
the negative electrode may be provided with an 'anti-polar' mass, i e
besides being loaded with the normal negative mass (cadmium or iron)
is also loaded with an anodic oxidisable oxide (for example nickel
2-hydroxide, cobalt 2-hydroxide etc) or with an anodic oxidisable
metal (which is nobler than that of the normal negative mass), for
example with copper powder In this case the nickel 2-hydroxide or the
copper in the electrode acts as an acceptor for oxygen formerly
produced upon reversal of polarity of the electrode In order to
improve the efficiency of the 'anti-polar' mass employed there is
added thereto inter alia a sufficiently large quantity of conductive
material (for example, graphite or nickel flakes.

Alternatively, according to the invention both electrodes of the
element may be provided with normal and also with anti-polar masses, i
e the positive electrode with a cathodic reducible oxide and the
negative electrode with an anodic oxidisable oxide or metal which is
nobler than the metal employed as the normal negative and which can
only display its effectiveness after discharge of the normal negative
mass.
The plates of alkaline accumulators commonly consist of a structure
such as, for example, a number of small tubes joined to form a plate,
or a body of sintered metal, which provides a number of pockets or
pores which contain the active mass The aforesaid 'anti-polar' mass
may be mounted in separate pockets or pores or in a separate dlate
connected to the plate carrying the active mass Alternatively, the
'anti-polar' mass may be in admixture with the active -mass Thus for
example the active mass and the 'anti-polar' mass may be deposited in
the pockets or pores of the electrode carrier by precipitation from a
common solution 60
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* Accessibility
* Legal notice
* Terms of use
* 5.8.23.4; 93p
* GB784852 (A)
Description: GB784852 (A) ? 1957-10-16
Organic compounds of zirconium and their preparation
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The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in

particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
784,852 Date of Application and filing Complete Specification Oct 12,
1953.
&, rr P L | No 28009/53.
Application made in Germany on Oct 11, 1952.
Application made in Germany on Sept 17, 1953.
Complete Specification Published Oct 16, 1957.
Index at Acceptance:-Classes 2 ( 3), C 1 E Si K( 2: 8: 9), C 2 83 (A
1: F: G 1), C 3 A 8, C 3 AO 10 A( 1: 2), C 3 AO 10 A 4 (a: IS: C: D:
L), C 3 A 10 ASAI, C 3 A 13 A 1 (A 1: C), C 3 A 13 A 3 A 1 (A:
B: C), C 3 Ai 3 A 3 A( 2: 4), C 3 A 13 A 3 (B 1: C), C 3 A 13 C( 3 A:
9: 10 F), C 3 AI 4 B(I: 5), C 3 CS(A 1: C 5: E 2), C 3 C 8; and 2 (
5), R 7 P.
International Classification: -C 07 f C 08 g.
COMPLETE SPECIFICATION
Organic Corapounds of Zirconiurn and their preparation We, FARBWERKE
HOECHIST A Kl Ti ENGESELLSCHAFT vormals Meister Lucius & Bruining, a
body corporate recognised under German law, of Frankfurt (Mv)-Htchst,
Germany, do hereby declare the invention, for which we pray that a
patent may be granted to us, and the method by which it is to be
performied, to be particularly described in and by the following
statement: The present invention relates to zirconium compounds and a
process of preparing them.
It is known that zirconium compounds of carboxylic acids can be
prepared by causing carboxylic acids to act upon zirconium
tetrachloride As hydrogen chloride is formed during this reaction it
is necessary to protect the metal parts of the reaction vessels
against the attack of this product Sulphinic acids cannot be reacted
with zirconium tetrachioride as the hydrogen chloride produced during
the reaction has a decomposing effect upon the former compounds.
According to the present invention zirconium compounds containing acid
radicals of carboxylic or sulphinic acids can be obtained by reacting
zirconium alcoholates as hereinafter defined, if desired in the
presence of inert solvents or diluents, with carboxylic or sulphinic
acids and, if desired, by heating the reaction product to an elevated
temperature.
The reaction can also be carried out in such a manner that one of the
components is first reacted with a part of the other component and the
remainder of the latter is added when the reaction product is heated
at an elevated temperature.
The normal reaction temperatures range from 0 C to 150 C, preferably

from 20 C to 100 C The higher temperature to which the reaction
product may be heated preferably ranges between 50 C and 200 C If
solvents are used which boil below the reaction temperature, the
operation must be carried out under pressure in a closed vessel.
When 1 mol of a zirconium tetra-alcoholate is reacted with 4 mols of
carboxylic or sulphinic acid, the tetra-zirconium salt of the
respective acid is obtained If less than 4 mols of acid are used,
acylated zirconium alcoholates of the formula Zr (S)n (OR)4-_ are
formed, wherein S represents an acyloxy radical of a carboxylic or
sulphinic acid, R is the residue of the alcoholate group, especially
an alkyl radical, and N stands for an integer greater than zero and
smaller than 4 On heating, these acylated zirconium alcoholates
condense to yield products of high molecular weight which probably
have a chain-like or reticular structure The number of the alcoholate
or acid groups present may vary with the chosen molar ratio of the
components and with the reaction conditions The term "alcoholate" is
used herein to denote " phenolates" as well as "alcoholates ".
As carboxylic acids there are suitable, for instance, aliphatic
carboxylic acids such as formic acid, acetic acid or butyric acid;
cycloaliphatic carboxylic acids such as cyclohexane carboxylic acid,
and aromatic carboxylic acids such as benzoic acid or naphthoic acid
As suiphinic acids may be mentioned aliphatic sulphinic acids such as
ethane sulphinic acid, butane sulphinic acid, cyclohexane sulphinic
acid, benzene sulphinic acid and naphthalene sulphinic acid.
Higher aliphatic and cycloaliphatic carboxylic and sulphinic acids are
especially suitable, such as lauric acid, stearic acid, oleic acid,
fatty acids obtained by oxidation of hydrocarbons and also mixtures
thereof, naphthenic acids, resin acids, montanic acid, and sulphinic
acids which are prepared in known manner from the sulphochlorination
products of natural and synthetic diesel oils.
As zirconium alcoholates there come into consideration such
alcoholates as are derived from aliphatic alcohols such as methyl
alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, amyl
alcohol, hexyl alcohol and octyl alcohol.
784,852 Zirconium alcoholkes containing, per equivalent of zirconium,
less than 1 equivalent ol organic radicals bound through oxygen in the
manner of alcohoiates may also be used for the reaction.
Particularly valuable reaction products are obtained by reacting in
amounts based on 1 equivalent of zirconium, about O 1-0 3 equivalent
of monocarboxylic acid, if desired in successive portions, with a
zirconium alcoholate containing, per equivalent of zirconium, about 0
5-0 9 equivalent of organic radicals bound to zirconium through oxygen
in the manner of an alcoholate.
As organic radicals which are bound to zirconium through oxygen in the

manner of an alcoholate there may be mentioned aliphatic, alicyclic,
aromatic, aliphatic-aromatic and heterocyclic radicals, which may be
interrupted by non-acid groups such as the keto group, or by oxygen or
sulphur atoms or by nitrogen atoms carrying a hydrogen atom or an
organic radical or may be substituted by halogen atoms, ester groups
or amino groups.
Examples of organic radicals are methyl, ethyl, chlorethyl,
dimethylaminoethyi, isopropyl, butyl, octyl, octadecyl, cyclohexyl,
phenyl, naphthyl, benzyl: phenylethyl, furfurylmethyl, radicals of
compounds capable of enolization such as acetyl-acetone and
acetoacetic ester, radicals of aliphatic glycols of higher molecular
weight than glycol, such as 2:5 hexandiol or diethylene glycol and
also mixtures of these radicals Particularly valuable starting
materials are such zirconium alcoholates as contain, per equivalent of
zirconium, about 0 5-0 9 equivalent of organic radicals bound in the
manner of an alcoholate.
The remaining valencies of the zirconium, that is to say those which
are not bound through oxygen in the manner of an alcoholate to an
organic radical, may be satisfied, for example, by oxygen linked in
chain fashion to further zirconium atoms and/or by inorganic radicals
such as halogen and hydroxyl or by organic acid residues, for
instance, acetic acid residue In general, the advantage of these
starting materials resides in the fact that the organic radicals bound
in the manner of an alcoholate through oxygen can be split off by the
action of organic acid substances Generally, they can be split off
merely by the action of moisture.
For this reason, it may be of advantage in manufacture on an
industrial scale to use the alcoholates in the form of their carbon
dioxide and sulphur dioxide addition products, wihich are stable to
moisture, or after stabilization by means of volatile organic
substances which contain a carbohyl group and are capable of forming
chelate compounds with the alcoholates.
As zirconium compounds containing, per equivalent of zirconium, less
than one equivalent of organic radicals bound in the manner of an
alcoholate through oxygen, there may be mentioned, for instance, such
zirconium alcoholates as can be obtained by the thermal and hydrolytic
treatment of normal zirconium tetra-aicoholates accompanied by the
splitting 70 off of parl of thle alkoxy groups, and min most cases
probably with the linking together of zirconium atoms in chain fashion
through oxygen atoms.
Among these zirconium alconolates there 75 may be mentioned, for
example, the polyineric zirconium butyiates obtained by thermal
treatment by a process analogous to the process for the preparation of
titanium alcoholates as described by Kraitzer (Journ Oil and 80 Colour

Chemists' Assn, volume 31, ( 1948), pa,,_ 4 k 3); Lurthernore there
may be cited the dimeric or polymeric zirconium isopropyiate obtained
by the hydrolytic treatment of zirconium tetraisopropylate with O 5
mol or 1 85 mol of water in isopropanol solution according LO Lh
process described by Winter which is likewise known for the
preparation of titanium alcoholates (Canadian Paint and Varnish Mag,
volume 25, pages 12-19 90 ( 1951)).
There may also be used zirconium alcoholates containing less than four
alkoxy groups which are obtained by reacting Zr OC 1,pymieine complex
compounds with slightly 95 hydrous alcohols and with ammonia gas, by a
process analogous to that using anhydrous alcohols as described by
Bradley (Journ.
Chem Soc London ( 1950), page 3450; ( 1952) page 2032) 100 As
zirconium alcoholates containing halogen atoms there may be mentioned,
for instance, zirconium chlortrialcoholates obtained from zirconium
tetra-aicoholates and actyl chloride and zirconium dichlordiethylates
obtained 105 from zirconium tetrachloride and ethanol according to the
process described by Bradley (Journal of the Chemical Society, Lond, (
1950), page 3450; ( 1952) page 4609).
There may also be used for the reaction 110 with the acids, mixtures
of zirconium alcoholates having a reduced content of alkoxy groups or
mixtures of these alcoholates with normal zirconium tetra-alcoholates
They may also be used for the reaction with the acids in 115 ithe form
of their alkoxo-acids (as hereinafter defined) and/or in a form
stabilized against moisture in known manner by means of volatile
organic compounds such as acetyl acetone or acetoacetic ester which
contain a carbonyl 120 group which compounds are capable of forming
chelate compounds with zirconium alcoholates, ( of F Schmidt,
Zeitschrift fir angewandte Chemie, volume 64 ( 1952) page 538).
The reaction may also be conducted in the 125 presence of a volatile
organic compound containing a carbonyl group which compound is capable
of forming a chelate compound with zirconium alcoholate.
Insofar as the reaction products still con 130 784,852 tain alkoxy
groups which can be split off by moisture, they can be stabilized
against decomposition by moisture, particularly at room temperature,
by addition of or reaction with a volatile organic compound containing
a carbonyl group which compound is capable of forming a chelate
compound with zirconium alcoholate, such as acetyl acetone, and
acetoacetic ester.
By the use of different zirconium alcoholates the properties of the
organic zirconium compounds obtained can be adapted to the intended
use.
The alkoxo-acids which are mentioned above and may be used in the
present process are compounds which have been formed by the addition

of alkali metal alcoholate and alcohol to the zirconium alcoholates,
for example, the compound of the following formula -Na Hi Zr (OC Hs)j
This compound has been described for instance by Meerwin and Bersin in
the Annalen der Chemie, volume 476 ( 1929) page 113.
As inert solvents or diluents for the reaction there come into
consideration, for instance, hydrocarbons or chlorinated hydrocarbons
such as benzine, benzene, carbon tetrachloride or trichlorethylene;
low-boiling esters such as ethyl acetate or amyl acetate; dialkyl
ethers such as diethyl ether; cyclic ethers such as dioxane or
tetrahydrofurane, and also anhydrous, aliphatic alcohols, which
contain between one and four carbon atoms.
The reaction products obtained are, according to the chosen molar
ratio of the reaction components and the nature of the acid, of an
oily, semi-solid, wax-like or solid consistency.
They are soluble in numerous organic solvents and are compatible with
plasticisers They may be used in many industries such as the
lubricant, fuel, paint and varnish industries.
The following examples illustrate the invention, the parts being by
weight:EXAMPLE 1.
271 parts of zirconium tetraethylate are dissolved in 2000 parts of
anhydrous ethyl alcohol, and 240 parts of glacial acetic acid are
added in portions while stirring From the clear solution of the
zirconium tetra-acetate thus formed, the alcohol is removed by
distillation under reduced pressure 320 parts of zirconium
tetra-acetate are obtained as white crystals which are easily soluble
in cold ethyl alcohol or water.
Instead of zirconium tetraethylate, there may also be used 327 parts
of zirconium tetraisopropylate or 383 parts of zirconium
tetrabutylate.
EXAMPLE 2
anhydrous benzene mixed with 500 parts of anhydrous ethyl alcohol and,
at 10 C, there are added in portions, while stirring, 274 parts of
commercial stearic acid (solidification point: 52 C, molecular weight:
274) The clear solution is then stirred for another hour at 60 C and
subsequently the solvent is distilled off at this temperature under
reduced pressure The reaction product consists of a viscous oil which
has a semi-solid consistency in the cold It is soluble in cold carbon
tetrachloride, benzene, and benzine.
If, instead of stearic acid, a commercial sperm oil fatty acid (acid
number= 212, saponification number= 214, iodine number= 71) is used
and otherwise the same method of working is adopted as described
above, a viscous oil is likewise obtained which solidifies in the cold
to give a soft wax The latter is soluble in cold carbon tetrachloride,

benzene, and benzine.
EXAMPLE 3
anhydrous benzene 85 mixed with 500 parts of anhydrous ethanol and, at
20 C, 109 parts of commercial stearic acid (solidification point: 52
C, molecular weight: 274) are added in portions while stirring The
clear solution is then boiled for 90 another hour under reflux and
subsequently the solvent is distilled off Finally the distillation
residue is heated for one hour at about C The reaction product is a
condensation product of zirconium ethylate and 95 stearic acid which,
according to analysis, contains about 0 4 mol of stearic acid and 1 6
mols of ethoxyl per zirconium atom In the hot it is a viscous oil
which solidifies in the cold then showing a waxy consistency At 100
room temperature it is soluble in carbon tetrachloride, xylene, and
test benzine.
If, instead of commercial stearic acid, 550 parts of commercial sperm
oil fatty acid (acid number= 211, saponification number= 214, 105
iodine number= 71) are used and otherwise the same method of working
is adopted as described above, whilst applying a temperature of 150 C
for heating the distillation residue 5 a wax-like zirconium compound
is obtained 110 showing the same solubility pro Derties.
EXAMPLE 4
136 parts of zirconium tetraethylate arc dissolved in 1000 parts of
anhydrous xylene and there are added dropwise at room temperature, 115
while stirring, 15 parts of glacial acetic acid.
The clear solution is boiled under reflux for another hour and
subsequently the solvent and the split off ethanol are distilled off
The reaction product, a condensation product of 120 zirconium ethylate
and acetic acid, which, according to analysis, contains about 0 5 moi
of acetic acid and 1 8 mols of ethoxyl per zirconium atom, consists of
a crystalline white mass melting at 230 C The ethoxyl con 125 tent
found by analysis shows that in the heating further condensation has
taken place The 784,852 mass obtained is soluble in aliphatic and
aromatic hydrocarbons.
EXAMPLE 5
To 327 parts of zirconium tetra-isopropylate dissolved in 1000 parts
of carbon tetrachloride, are added, while stirring, 188 parts of
dodecyl sulphinic acid On heating, a clear solution of a condensation
product of zirconium isopropylate and dodecyl sulphinic acid is formed
which is boiled under reflux for another hour Tht solvent and the
split off isopropanol are then distilled off, finally under reduced
pressure at a temperature of about C The reaction product is a
condensation product of zirconium isopropylate and dodecyl sulphinic
acid which contains about 0.8 mol of dodecyl sulphinic acid and about

2.5 mols of isopropoxyl per zirconium atom.
In the hot it is a viscous oil which solidifies slowly in the cold and
finally shows a waxlike consistency It is soluble at room temperature
in carbon tetrachloride, xylene, and test benzine.
If, instead of dodecyl sulphinic acid, the equivalent quantity of
benzene sulphinic acid is used and the same working method is adopted
as described above, a condensation product of zirconium isopropylate
and benzene sulphinic acid is obtained In the hot it is a viscous oil
which solidifies in the cold to show a wax-like consistency and which
is soluble in xylene.
EXAMPLE 6
To 327 parts of zirconium tetraisopropylate dissolved in 1000 parts of
carbon tetrachloride, are added, while stirring, 140 parts of lauric
acid A condensation produdt of zirconium isopropylate and lauric acid
is formed while heat is generated and isopropanol is split off The
clear solution is boiled under refiux for another hour and the
isopropanol is distilled off The reaction product is a condensation
product of zirconium isopropylate and lauric acid which contains 0 7
mol of latric acid and 2 3 mols of isopropoxyl per zirconium atom In
the hoa it is a viscous oil, i'hilst in the cold it has a wax-like
consistency; it is soluble in perchlorethylene.
If, instead of lauric acid, 37 parts of benzeic acid are used and
otherwise the same method of working is adopted, a condensation
product of zirconium isopropylate and benzoic acid is obtaintd which
contains 3 mool of benzoic acid and about 2 7 mols of isopropoxyl per
zirconium atom In the hot it is a viscous oil which solidifies in the
cold to show a wax-like consistency; it is soluble in xylene.
EXAMPLE 7
327 parts of zirconium tetraisopropylate are melted, while stirring,
with 800 parts of lauric acid at a temperature of about 120 C, whereby
the split off isopropanol is distilled off and thus recovered The
zirconium tetralaurate formed is stirred for a short time under
reduced pressure at 140 C An oil is obtained which solidifies at about
140 C.
to a wax-like substance and which is soluble in carbon tetrachloride,
benzene, and test benzine.
If, instead of 327 parts of zirconium isopropylate, 383 parts of
zirconium tetra isobutylate are used and the same working method is
adopted as described above, the same result is obtained.
EXAMPLE 8
To 327 parts of zirconium tetra isopropylate dissolved in 1000 parts
of carbon tetrachloride, are added, while stirring, at about C, 270
parts of commercial stearic acid 80 (solidification point 52 C,
molecular weight:

270) A clear solution of a mono-stearic acid condensation product of
zirconium isopropylate is formed, while isopropanol is split off 60
parts of glacial acetic acid are then 85 added dropwise at 50 C while
stirring A clear solution of a zirconium
monostearatemonoacetate-diisopropylate is formed, while further
isopropanol is split off The solvent is then distilled off, finally
under reduced 90 pressure 510 parts of a viscous oil are obtained
which solidifies in the cold to give a wax and which is soluble in
benzene, carbon tetrachloride, and test benzine.
If double the amounts of commercial stearic 95 acid and glacial acetic
acid are used and otherwise the same method of working is adopted as
described above, a simple distearic acid and diacetic acid
condensation product of zirconium isopropylate is obtained that is zir
100 conium distearate-diacetate In the hot it is a viscous oil which
solidifies at 25 C to a wax-like substance It is soluble in
prchlorethylene, xylene and test benzine.
EXAMPLE 9 105
552 parts of a dimeric zirconium isopropylate, prepared in the manner
described by Cow and Winter for titanium alcoholates (Fette und
Seifen, 1953, page 431) by the action of 1 mol of water in an
isopropanol solution of 110 1 per cent strength at room temperature
upon 2 mols of zirconium tetra-isopropylate dissolved in the same
amount of carbon tetrachloride, and by distilling off the solvent
under reduced pressure, are dissolved in 1000 parts 115 of carbon
tetrachloride To the solution produced there are added while stirring
and at about 400 C, 270 parts of commercial stearic acid
(solidification point 52 C, molecular weight 270) and the clear
mixture is then 120 heated for another hour at about 60 C.
Finally the solvent and the split off isopropanol are distilled off
under reduced pressure.
The reaction product is a wax which solidifies at about 450 C and is
easily soluble in 125 xylene, test benzine, and carbon tetrachioride.
784,852 EXAMPLE 10
300 parts of a polymeric zirconium isopropylate, prepared by a process
analogous to that described by Bradley, which used anhydrous alcohols
(Journal of the Chemical Society, Lond, ( 1952), page 2032), by
reacting the Zr O C 12-pyridine complex compound with isopropanol of
98 per cent strength in benzene and ammonia gas and by subsequently
filtering off the ammonium chloride with suction and distilling off
the solvent, are dissolved in 1000 parts of perchiorethylene To this
solution are added, at 30 C while stirring, 200 parts of lauric acid
and the clear solution thus formed is boiled for another hour under
reflux The solvents are then distilled off under reduced pressure A
wax is obtained which has a solidification point of about 30 C and

which is soluble in xylene, perchlorethyltne, and test benzine.
EXAMPLE 11
210 parts of a polymeric zirconium isopropylate prepared in the manner
described in Example 9 by reacting 1 mol of water with only 1 mol of
zirconium tetraisopropylate, are dissolved in the same weight of
perchlorethylene and there are added, at about 50 C, while stirring,
90 parts of commercial stearic acid (molecular weight 270,
solidification point 52 C) The clear mixture is boiled for one hour
under reflux and the solvent and the split off isopropyl alcohol are
then distilled off The reaction product is a wax which melts at about
35 C and which is easily soluble in xylene, test benzine, and carbon
tetrachloride.
If, instead of stearic acid the same amount -of benzoic acid is used
and otherwise the same method of working is adopted, a similar wax is
obtained which solidifies at 40 C.
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