DENTURE BASE

RESINS
DR NIVEDITHA N
I MDS
DEPARTMENT OF PROSTHODONTICS
AECS MAARUTI DENTAL COLLEGE
 CONTENTS
 Introduction
 History
 Requirements
 Classification
 Composition
- heat cure
- autopolymerising resin
-other resin materials
 Aspects of manipulation
 Recent advances(modified acrylics)
 Review of literature
 Summary and conclusion
 References
 INTRODUCTION
 Denture base is that part of a denture that rests on the
foundation tissues and to which teeth are attached. Although
individual denture bases may be formed from metals or metal
alloys, the majority of denture bases are fabricated using
polymers.
 HISTORY
 1851 – Vulcanite was developed.

 1853-1st denture base from vulcanite

was constructed by Nelson Charles
Goodyear,
 1891- use of vulcanite as a denture base
material was considered “universal”.
 1869- Celluloid was introduced,
developed from plant framework.
It had natural gingival colour but short
shelf life.therefore, NEW MODE
CONTINOUS combination product, of
rubber denture base material, a
celluloid gum work area and porcelain
teeth.
1910-1940
 Other polymers: vinyl acrylics, Polystyrene, Epoxy,
Nylon, Vinyl styrene, Polycarbonates, Polysulfonates
-unsaturated Polyester, Polyurethane, Polyvinyl
acetate- ethylene, Hydrophilic polyacrylate etc

 1930-1940 the Phenol formaldehyde products were

1st to compete with vulcanite.
 Self cure were introduced after world war II.
 1936- Vernonite or poly
methylmethacrylate(PMMA).1st practical
replacement for Vulcanite.
 1946- 95% of dentures were made with Vernonite
 Requirements
1. Biological:
- non toxic and non-irritant.

2. Chemical:
- inert , in-soluble and non-absorbent.

3. Physical:
- Aesthetically satisfactory.
- The softening temperature should be higher than the
temperature of liquids and food ingested.
- Dimensionally stable.
- Low value of specific gravity or density.
 - High value of thermal conductivity: to maintain the healthy mucosa,
and to retain normal reaction to hot and cold stimuli.

4. Mechanical properties:
- A high value of modulus of elasticity- For greater rigidity.
- A high value of elastic limit to prevent permanent deformation.
- A combination of both above would allow the base to be fabricated
in thin sections.
- Sufficient flexural strength to resist fracture.
- An adequate fatigue life and a high fatigue limit.
- Good impact strength.
- Sufficient abrasion resistance to prevent excessive wear.
5. Miscellaneous
- Relatively inexpensive.
- Easy to manipulate and fabricate.
- Easy to clean.
- Easy to repair.
 CLASSIFICATION

I. According to ISO 1567

Type Class Description

1 1 Heat processing (powder and liquid)

1 2 Heat processing (plastic cake)
2 1 Self cure (powder and liquid)
2 2 Self cure (powder and liquid pour type
resins)
3 - Thermoplastic blank or powder
4 - Light-activated materials
5 - Microwave materials
II. According to material system
1. Metallic – stainless steel denture base
2. Non-metallic – acrylic resins,vinyl resins etc.

III.According to method of activation

3. Thermal – heat cure acrylics
4. Chemical- self cure acrylics
5. Light activated
6. Microwave energy
IV. According to mode of polymerization
1.Addition polymer – e.g. acrylic resins, polyvinyl
chloride, polymethyl methacrylate
2.Condensation polymer – e.g. bakelite, nylon

V.According to usage
*Temporary denture base resin
-shellac base plate
-self cure acrylics
-injection molded resins
*Permanent denture base resin
-heat cure denture resins
-light cure resins
 ACRYLIC RESIN MATERIALS

Polymerisation reaction:
The polymerisation of PMMA involves the
conversion of low molecular weight monomer to
high molecular weight polymer.

Free radical addition polymerisation which

involves initiation ,propagation and termination.
 Initiation

Free radical

Monomer molecule
 Induction or initiation period is the time during which the molecules of the initiator becomes
energized or activated and start to transfer the energy to the monomer.
• Any impurity present increases the length of this period. The higher the temperature, the
shorter is the length of the induction period.
• The initiation energy for activation of each monomer molecular unit is 16000-29000 calories
per mol in the liquid phase.
• There are three induction systems for dental resins

Chemical activation
Heat activation Light activation
This system consists of at least two
Most denture base resins are In this system, photons of light energy
reactants, when mixed they undergo
polymerized by this method, activate the initiator to generate free
chemical reaction and liberate free
e.g. the free radicals liberated by radicals, e.g. camphorquinone and an
radicals,
heating benzoyl peroxide will initiate amine will react to form free radicals,
e.g. the use of benzoyl peroxide and
the polymerization of methyl when they are irradiated with visible
an aromatic amine (dimethyl-p-
methacrylate monomer. light.
toluidine) in self-cured dental resins
Propagation

Once the growth has started only 5000 to

8000 calories per mole are required, the
process continues rapidly and is
accompanied by evolution of heat.
Theoretically, the chain reactions should
continue with evolution of heat until all
the monomer has been changed to
polymer. In reality however, the
polymerization is never complete.
 Termination

Termination
The chain reactions can be
terminated either by direct coupling
of two chain ends or by exchange of a
hydrogen atom from one growing
chain to another.
Chain transfer

Chain transfer occurs when a free radical

approaches a methylmethacrylate molecule and
donates a hydrogen atom to the
methylmethacrylate molecule. This causes the
free radical rearrangement to form a double
bond and become unreactive and the
methylmethacrylate monomer to form a free
radical that can participate in a chain-
propagation reaction.
Composition of heat cure denture base resin
Powder
a. Prepolymerised polymethyl methacrylate in the form of
beads or granules.
b. Initiators – Benzoyl peroxide (0.5-1.5%), to initiate the
polymerization of the monomer
c. Plasticizer – Dibutylpthalate (8-10%), increases the rate of
dissolution of polymer in monomer.
d. Pigments – Cadmium sulfide (pink), Mercuric sulfide
(red),Rouge/ Ferric oxide(brown).
e. Synthetic fibers: Acrylic or nylon to simulate small capillaries
f. Inorganic fillers -Glass fibers, zirconium silicate,
silicone carbide etc. to increase the stiffness and decrease the
coefficient of thermal expansion.

g. Opacifiers-Heavy metal compounds, e.g. salts of Barium and

Strontium, zinc or titanium oxide

Liquid
a. Methyl methacrylate monomer- It has a limited shelf life

b. Inhibitor- Hydroquinone(0.006%), added to improve the shelf

life of monomer and prevent premature polymerization.

c. Cross linking agent- glycol dimethacrylate, it improves the

mechanical properties, more resistant to surface crazing.
d. Plasticizer- Dibutyl pthalate, to produce a softer and
more resilient polymer.
Gel types – e.g. Vinyl acrylics
•Liquid and powder have been mixed to form a gel and
shaped into a thick sheet.
•Chemical accelerators cannot be used.
 Self cure resins:
Dispensed as powder and monomer liquid.
Composition:
Polymer: PMMA in the form of beads.
Copolymer-PEMA
Initiator :(< 2%) Benzoyl peroxide
Plasticizer: dibutyl phthalate
Colour pigments: salts of Mercury and Iron
Dyed synthetic fibers
Inorganic particles : glass fibers, Zirconium Silicate
Radio-Opacifiers: salts of Barium .
 Monomer:
Methylmethacrylate monomer.
Inhibitor- hydroquinone
Cross linking agent- glycol dimethacrylate
Plasticizer- dibutylpthalate
Activator- dimethyl para toludine
Setting reaction:
PMMA +initiator+MMA+inhibitor+activator
(powder) (liquid)

free radicals(R°)

R° + M RM° Liberation of heat

 Properties:
 Free of residual monomer- 3-5%
 Polymerisation of self cure is never completed.
 The effects of free residual monomer: released from the denture thus
irritate the mucosa.
 Shorter working time due to gradual increase in viscosity.
 Curing is done at room temperature. So better fit and more stable.
 The color stability is not good.
 Easy to manipulate.
 Advantages:
Eliminates the processing stresses.
Less thermal contraction.
Disadvantages:
More residual monomer
Low mechanical properties.
Colour instability.

Uses: Occasionally used for denture bases.

-Preparation of special trays.
-Denture repairs, relining and rebasing.
-For removable orthodontic appliances.
property Heat cure Self cure

Method of heat Chemical

activation
Polymerisation Heated to 60 to On mixing
reaction 70°C

Degree of high low

polymerisation

Mechanical Superior inferior

Compressive strength(Mpa) 75 65

Impact strength(MPa) 1.5x106 at 17.2MPa Less

Tensile strength(MPa) 65 lesser

Residual monomer .2-.4% 3-5%

Thermal shrinkage higher Lesser

crazing greater Better dimensional stability

Water solubility 0.02 mg/cm 2
0.05mg/cm 2

Water sorption(mg/cm 2) 0.6 0.7

Aesthetic quality Good color stability No good color stability

Processing shrinkage 0.53% 0.26%

TECHNICAL CONSIDERATIONS

Dentures are usually fabricated by one of the following techniques

1. Compression molding technique (usually heat activated resins).

2. Injection molding technique (heat activated resins).

3. Fluid resin technique (chemically activated resins).

4. Visible light curing technique (VLC resins).

 Aspects of manipulation

1. Preparation of the mould

2. Selection of separating medium
3. Powder liquid ratio
4. Polymer monomer interaction
5. Dough forming time
6. Packing
7. Bench curing
8. Polymerization cycle
 1. Preparation of the mould

CAP

COPE

DRAG
2. Selection of separating medium
Used to separate the denture base material from the mould
surface.
Formerly, Tin foil was used, but it was a time consuming
and difficult process.
Causes: a. Dimensional inaccuracy
b. Poor reproduction of details
Tin foil substitutes:
-Cellulose lacquers
-Evaporated milk
-Solutions of alginate compounds
- Soap
- Sodium silicate
- Starch
The most commonly used separating medium are water soluble alginates. When applied
to dental stone surfaces, these solutions produce thin, relatively insoluble calcium
alginate films. These films prevent direct contact of denture base resins and the
surrounding dental stone, thereby eliminating undesirable interactions.
Composition:
1. Sodium/potassium alginate- 2-3%
2. Di/tri sodium phosphate- 0.7%
3. Preservatives- 0.3%
4. Glycerin- 4%
5. Alcohol- 7%
6. Balanced with water- 85%
Setting reaction:
Potassium alginate + calcium sulphate calcium
alginate + potassium sulphate
Functions:
1. To prevent the diffusion of water from the mold into
the unpolymerized packed dough.
2. To prevent the diffusion of the monomer from the
unpolymerised packed dough into the mould material.
Precautions: The coating should be uniform.
-Dewaxing must be done thoroughly.
-The resin teeth should not be coated.
 Powder: liquid ratio

It controls the workability of the mix and the dimensional

change on setting.
•Too much powder: Under wetting of the polymer beads
•Too much of monomer-Excessive Polymerisation
shrinkage and loss of quality of fit.
•To reduce the Volumetric Polymerisation shrinkage from
21% to 7% and linear shrinkage to 0.5%
- Use of prepolymerised resin is recommended
- 3:1 polymer and monomer ratio.
 Polymer monomer interaction
The powder is slowly added to the liquid to get a
workable mass which passes thro five distinct stages:
(1) Wet, sand like stage
(2) Stringy stage/ a tacky fibrous stage.
(3) A smooth Dough like stage:On molecular
level:Increase in no. of polymers chains, a large
amount of undissolved polymer remains.
clinically, no longer tacky and does not stick to mixing
spatula.The latter phases of this stage is ideal for
compression moulding.
(4) Rubbery or elastic stage:dissipation of monomer.
clinically, rebound and stretches.
(5) Stiff stage:evaporation of free monomer.
clinically, the mixture appears dry and is resistant
to mechanical deformation.
DOUGH FORMING TIME:
The time required for resin mixture to reach a dough like
stage. According to ADA-12 it is less than 40 mins &
clinically it reaches in 10 mins.
WORKING TIME: According to ADA-12,the dough to remain
moldable for atleast 5 mins.
 Packing
The dough is packed into the mould
cavity.
•Packed at sandy or stringy stage,
too much monomer will be present
between the powder particles.
•If too early : porosity.
•If done at rubbery or stiff stage, material too viscous
to flow.
•Over packing: Excessive thickness and mal positioning of prosthetic teeth.
•Under packing: Noticeable porosity.
•The acrylic dough is packed into the flask by use of pneumatic, hydraulic or
mechanical press.
 Trial closure
The acrylic dough is packed into the flask in slight excess. The excess is removed
during trial packing with a damp cellophane or polyethylene film used as a separator
for the upper half of the flask. The closing force is applied slowly during the trial
packing to allow the excess dough, known as ‘flash’ . Before final closure, the
separating film is removed and discarded.

BENCH CURING
 After the final closure of the flask , it is allowed to stand for 1 hour.
 Objective:
 For more uniform dispersion of monomer throughout the mass.
 It provides a longer exposure of resin teeth to the monomer in the dough,
producing a better bond of the teeth with the base material.
 Permits an equalization of pressures throughout the mold
Polymerisation cycle or Curing cycle:
The heating process used to control polymerisation is termed
polymerisation cycle.This process should be well controlled
to avoid the effects of uncontrolled temperature rise, such as
boiling of the monomer, or denture base porosity.The
following techniques are there:
1.Involves processing the denture base resin in a constant
temperature water bath at 74°C(165°F) for 8 hours or longer,
with no terminal boiling treatment.(slow curing)
2.Processing in a 74°C water bath for 8 hour and then
increasing the temperature to 100°C for 1 hour.
3.Processing the resin at 74°C for approximately 2 hour and
increasing the temperature of the water bath to 100°C and
processing for 1hr.(fast curing)

BENCH COOLING:
It is cooled slowly as rapid cooling may result in warpage
because of differences in thermal contraction of resin and
investing stone.
Bench cooled for 30mins and subsequently immersed in cool
tap water for 15mins.
 PROCESSING DEFECTS OF DENTURES

 Rough or irregular surface.

 Porosity
 Dimensional changes
 Processing stresses
 Crazing
 Fractures
 Denture warpage
 ROUGH OR IRREGULAR SURFACE

 Improper wetting of wax denture by plaster mix.

 Entrapment of air bubbles in investing plaster.
 Low liquid powder ratio.
 Incomplete dewaxing.
 Insufficient or improper coating of separating agent.
 delayed packing.
 Insufficient material in the mold.
 POROSITY
 Undesirable effect on the strength and optical, hygienic
properties. The causes are:
 Polymerisation shrinkage termed

 Contraction porosity-appear as irregular voids throughout,

and on the surface of denture.
causes:insufficient material, insufficient pressure.
 Gaseous porosity shows fine uniform bubbles. Particularly in
thicker regions.
 Localised porosity-improper mixing of components or early
packing.
 Granular porosity-granular effect on the denture
surface, due to low powder liquid ratio.
 opaque surface – when mixing vessel’s lid is not
covered.

Insuffiecint
mixing

Insuffient
pressure

Rapid heating
PROCESSING STRESSES
 Polymerisation shrinkage.
 Mechanical stresses on repeated drying and wetting
of the denture, causing alternate contraction and
expansion.
 During deflasking internal stresses are developed.
 Difference in the coefficient of thermal expansion
of acrylic resin and investing material.
 CRAZING FRACTURES
 May appear on the surface and has  Dentures may break:
weakening effect.  On impact(extra orally)
 Delayed packing.  Due to fatigue, form repeated bending of the
 Constant cycle of drying and wetting denture in service.(if parallel cracks).(intra
orally)
done by patient.
 Presence of notches.
 It is around the tooth neck
 Inadequate curing time.
 Difference in the coefficient of thermal
expansion of porcelain teeth and acrylic  Excessive grinding and polishing
resin.(1:10)
 Sudden cooling.

 During polishing .
 DENTURE WARPAGE

Denture warpage is the deformity or change of shape of the denture which can
affect the fit of the denture.
It is caused by a release of stresses incorporated during processing, curing
shrinkage, uneven or rapid cooling, improper deflasking.
Packing of the resin during the rubbery stage can also induce stresses. These
stresses are released subsequently
 During polishing, a rise in temperature can cause warpage
 Immersion of the denture in hot water can cause warpage
 Re-curing of the denture after addition of relining material, etc
 INJECTION MOULDING TECHNIQUE
In this technique, for injection of resin, a hollow sprue
connects the mould cavity created by wax boil out to an
external opening on the flask and a high pressure injection
cylinder is connected to the opening.
The pressure is maintained during the polymerisation cycle.
Equipment
This technique uses special equipment
including a special bath for curing.A sprue
hole and a vent hole are formed in the
gypsum mold with the help of sprue formers.
The soft resin is contained in the injector and
is forced into the mold space as needed. It is
kept under pressure until it has hardened.
Continuous feeding of the material under
pressure compensates for shrinkage. There is
no difference in accuracy or physical
properties as compared to compression
molding technique.
Advantage:
-increased dimensional accuracy.
-Elimination of trial closures.
-It can be used for microwavable and pour type resins.
Drawbacks:
-inadequate spruing will lead to under filled moulds.
-Expensive equipment.
-Injector is difficult to clean.
MANIPULATION OF AUTOPOLYMERIZING RESINS
1. Sprinkle on technique
2. Adapting technique
3. Fluid resin technique

POUR TYPE DENTURE RESINS/ POUR AND CURE

RESINS/ FLUID RESINS
 These are cold cure resins.
 Difference in the size of polymer.
 Slurry mixed which is poured into agar-hydrocolloid mold and allowed
to polymerize under pressure at 0.14MPa for 30 –45 mins..
 injection molding technique is used.
 FLUID RESIN TECHNIQUE
Employs a pourable resins, chemically activated resin.
Dispensed as a powder liquid system.(2.5:1by wt.)

A, Completed tooth B, Removal of teeth C, Preparation of sprues

arrangement positioned in arrangement from reversible and vents for the
a fluid resin flask. hydrocolloid investment. introduction of resin.
 D, Repositioning of the prosthetic teeth and master cast.

E, Introduction of
pour-type resin.

F, Recovery of the
completed prosthesis
Advantages:
- Improved adaptation to underlying soft tissues
Decreased probability of damage to prosthetic teeth and denture bases
during deflasking
Reduce material cost
Simple procedure
Disadvantages:
Noticeable shifting of teeth
Air entrapment within the denture base material
Poor bonding between the denture base material and teeth
Technique sensitive
 MICROWAVE ACTIVATED RESINS

 Electromagnetic waves.
 A special glass fibre reinforced plastic flask.
 Dewaxing is done in a microwave for 1.5 minutes.
 Processing technique: compression moulding.
microwave energy in an oven at 500-600W
curing time as short as 3 mins.
LIGHT ACTIVATED DENTURE
BASE RESINS
 Single component denture base resin
supplied in pre mixed sheet or rope
forms
 It is a composite having a matrix of
urethane dimethacrylate, microfine
silica and high molecular weight
acrylic resin monomer
a) Organic filler- acrylic resin beads
b) Activator- visible light
c) Initiator- camphorquinone
 The acrylic is polymerized in a light chamber with blue light of 400 to 500nm.

 The denture base rotates in the chamber.

 A bonding agent – mixture of acrylic monomers, including methyl methacrylate;cured by

visible light.

Advantages:
No flask required.
Short processing time.,Improved
fit, comparable impact strength &
hardness

Disadvantages:
High capital cost.
Inferior bond to resin denture.
Lower elastic modulus and
increase deformation.

Recently, they have been trying the use of lasers for polymerisation of resins.
 MODIFIED ACRYLICS
 Objective is to improve the impact strength, fatigue resistance, or
radiopacity.
 The impact strength or high impact strength materials -improved by
adding
-Elastomers: able to absorb energy.
-Use of acrylic-elastomer copolymer e.g. methylmethacrylate-butadiene
or methylmethacrylate- butadiene-styrene copolymers.
Increased by 10 fold.
Drawback is greater cost.
 ALTERNATIVE POLYMERS:
Polycarbonates and certain vinyl polymers.
Indications: allergic patient, when greater impact strength is required.
Processing: Injection molding.
So special equipment is required.

RAPID HEAT POLYMERISED RESINS OR HYBRID ACRYLICS:

polymerized in boiling water immediately after being packed into a denture flask.

procedure: after placing the denture in boiling water , boiled for 20

mins and then bench cooling .
The initiator is formulated from both chemical and heat activated
initiators to allow rapid polymerisation.
Polymerisation shrinkage-0.97-0.43% double the conventional
ones.
NEW ERA IN DENTURE BASE
RESINS: A REVIEW
Dr. Shikha Nandal Dr. Pankaj Ghalaut Dr. Himanshu Shekhawat Dr. Manmeet Singh Gulati

1. Reinforced resins
a. High impact resins
b. Fiber-reinforced
2. Hypoallergenic resins
3. Resins with modified chemical structure
4. Thermoplastic resins
5. Enigma gum toning in denture bases
HIGH IMPACT RESINS
 Rubber reinforced (butadiene-styrene polymethyl methacrylate).
 Rubber particles grafted to MMA for better bond with PMMA. They are so-called
because of greater impact strength & fatigue properties, hence indicated for patients
who drop their dentures repeatedly e.g. parkinsonism, senility.
 Available as powder-liquid system & processing is same as heat cure resins.
 E.g Lucitone 199 , D.P.I Tuff , fricke-high impact. Impact strength of D.P.I Tuff is
more than Lucitone 199.
FIBER REINFORCED RESINS
Primary problem with PMMA is low impact strength & low fatigue resistance. A study
by Johnston et al shows that 68% dentures fracture within few years of fabrication.
Fiber reinforcement result in a 1000% strength increase over non-reinforced (if there is
proper bonding)
a) METAL FIBER REINFORCED
b) CARBON / GRAPHITE FIBER REINFORCED
c) ARAMID FIBER REINFORCED
d) POLYETHYLENE FIBER REINFORCED
 e) GLASS FIBRES (HAVE BEST AESTHETICS)
Six mm chopped glass fibers with 5% fiber in combination with
injection moulding technique result in increase in transverse
strength, elastic modulus& impact strength.

COMPARISON OF IMPACT STRENGTH OF RESINS

REINFORCED WITH DIFFERENT FIBERS:
Polyethylene > glass > carbon > unreinforced.
B) HYPOALLERGENIC RESINS
Diurethane dimethacrylate, Polyurethane, Polyethylenterephthalate and
Polybutylenterephthalate. Hypoallergenic denture base materials exhibit significantly lower
residual monomer content than PMMA , thus act as alternatives to Poly Methyl Methacrylate
in allergic patients.
C) RESINS WITH MODIFIED CHEMICAL STRUCTURE
Addition of hydroxy-apatite fillers increases fracture toughness. Addition of Al2O3
fillers increases the flexural strength & thermal diffusivity that could lead to more
patient satisfaction

D) THERMOPLASTIC RESINS
This new procedure, during which a fully polymerized basic material is softened by
heat (without chemical changes) and injected afterwards, has opened up a new chapter
in making dentures.
ADVANTAGES OF
THERMOPLASTIC MATERIALS
Thermoplastic resins have many advantages over the conventional powder-
liquid systems.

 excellent esthetics with tooth or tissue colored materials

 comfortable for the patient.
 stable, have high fatigue endurance, high creep resistance, excellent wear
characteristics
 non-porous so no growth of bacteria, retains a slight amount of moisture to
keep it comfortable against gums.
 unbreakable, flexible & light weight
 safe alternative due to very little or no monomer content.
 relined & repaired by repressing the restoration.
 These include

 thermoplastic Nylon (polyamide),

eg: Valplast & flexiplast

 thermoplastic acetal,
( ideal material for pre-formed clasps for partial dentures, single pressed
unilateral partial dentures, partial denture frameworks, provisional bridges, occlusal splints,
and even implant abutments.)

 thermoplastic acrylic
eg:Flexite M.P.-very popular for bruxism appliances as well as dentures.

 thermoplastic polycarbonate.
E) ENIGMA GUM TONING
1) Custom shade matching of natural gingival tissue
using ‘Enigma’ colour tones.
2) Gives extra confidence to patient in appearance of
their dentures.
3) Available in Ivory, Light Pink, Natural Pink, Dark
Pink & Light Brown. Different colors are mixed to get
the desired gum tone.
 SUMMARY AND CONCLUSION

 Denture bases are responsible for artificial tooth fixation,stability

and distribution of masticatory forces over a large tissue bearing

area.So far acrylic resins are most commonly used and still the
research is going on the resins which will fill all the requirements
of dentist and patient.
 REFERENCES
 Anusavice Kenneth J.: Phillips Science of Dental Materials.
12th edition
 Basics of Dental Materials by John J Manappallil 4th edition

 NEW ERA IN DENTURE BASE RESINS: A REVIEW Dr. Shikha

Nandal Dr. Pankaj Ghalaut Dr. Himanshu Shekhawat Dr. Manmeet
Singh Gulati